KR101570585B1 - Hollow fiber membrane spinning nozzle, and method for manufacturing hollow fiber membrane - Google Patents

Abstract

The present invention relates to a hollow fiber membrane spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer, wherein the nozzle has a resin flow path for flowing a film-forming resin solution for forming the porous membrane layer, And at least one of the following (a) to (c) is satisfied: a liquid storage portion for storing a liquid, a liquid storage portion for storing a liquid, and a shaping portion for shaping the film-forming resin solution into a cylindrical shape. (a) The resin flow path is disposed so that the film-forming resin solution branches and merges. (b) retarding means for retarding the flow of the film-forming resin solution is provided in the resin flow path. (c) The liquid storage portion or the negative portion includes a branching and merging means of the film-forming resin solution. According to the present invention, it is possible to provide a hollow fiber spinning nozzle capable of suppressing occurrence of cracks along the axial direction in the hollow fiber membrane to be obtained even when the spinning speed is increased, and a method of manufacturing a hollow fiber membrane using the spinning nozzle.

Description

TECHNICAL FIELD [0001] The present invention relates to a hollow fiber spinning nozzle and a manufacturing method of the hollow fiber membrane,

The present invention relates to a hollow fiber spinning nozzle and a method for producing a hollow fiber membrane.

The present application is based on Japanese Patent Application No. 2010-261481 filed on November 24, 2010, Japanese Patent Application No. 2011-035631 filed on February 22, 2011, Japanese Patent Application No. 2011-035631 filed on March 2, Japanese Patent Application No. 2011-045040 filed on April 12, 2011, Japanese Patent Application No. 2011-088187 filed on April 12, 2011, Japanese Patent Application No. 2011-100140 filed on April 27, 2011 And Japanese Patent Application No. 2011-118086 filed in Japan on May 26, 2011, the content of which is incorporated herein by reference.

Water treatment using filtration membranes excellent in separability, compactness, and the like is attracting attention due to heightened interest in environmental pollution and strengthening of regulations. As the filtration membrane in the water treatment, a hollow fiber membrane having a hollow porous membrane layer is suitably used (for example, Patent Document 1). For example, hollow fiber spinning nozzles 1101 (hereinafter referred to as " spinning nozzles 1101 ") illustrated in Figs. 6 to 8 are used for manufacturing such hollow fiber membranes.

The spinning nozzle 1101 has a first nozzle 1111 and a second nozzle 1112. The spinning nozzle 1101 has therein a support passage 1113 through which a hollow support is passed and a resin passage 1114 through which a film-forming resin solution for forming a porous film layer flows. The resin flow path 1114 includes an introduction portion 1115 into which the film-forming resin solution is introduced, a liquid storage portion 1116 which stores the solution in the form of an annular circular cylinder in the form of a film-forming resin solution, Shaped portion 1117 which is formed in a cylindrical shape. The spinning nozzle 1101 is formed such that the hollow support is fed from the support supply port 1113a and is led out from the support outlet 1113b and the film forming resin solution is supplied from the resin supply port 1114a and discharged from the discharge port 1114b And is discharged in a cylindrical shape around the support.

In the spinning of the hollow fiber membrane by the spinning nozzle 1101, the film-forming resin solution discharged from the discharge port 1114b of the spinning nozzle 1101 is applied to the outside of the hollow support member simultaneously led out from the support member outlet 1113b do. Thereafter, the film-forming resin solution is solidified in the coagulation bath, and the hollow fiber membrane is produced through a process such as washing or drying.

Japanese Patent Application Laid-Open No. 2009-50766

However, the conventional spinning nozzle, such as the spinning nozzle 1101, has a starting point of the crack along the axial direction in the porous film layer formed on the outside of the support, if the spinning speed is increased to manufacture the hollow fiber membrane with low productivity and high productivity A phenomenon that the porous film layer formed on the outer side of the support body is cracked along the axial direction may occur when the hollow fiber membrane is deformed into a flat shape.

An object of the present invention is to provide a hollow fiber spinning nozzle capable of suppressing occurrence of cracks along the axial direction in an obtained hollow fiber membrane even when the spinning speed is increased.

The inventors of the present invention have examined in detail the problem of forming a crack along the axial direction in the porous film layer when the spinning speed is raised in the spinning by the conventional spinning nozzle such as the spinning nozzle 1101. As a result, (FIG. 8) in which the film-forming resin solution which is divided into two portions in the liquid storage portion 1116 and flows in an arc shape joins the portion on the opposite side to the introduction portion 1115 in the liquid storage portion 1116 , It has been found that a starting point of a crack along the axial direction is formed in the porous film layer. The inventors of the present invention have further studied and completed the present invention.

That is, one side surface of the hollow fiber spinning nozzle of the present invention has the following configuration.

[1] A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer,

And a resin flow path for flowing a film-forming resin solution for forming the porous film layer inside,

Wherein the resin flow path has a liquid storage portion for storing the liquid in which the film-forming resin solution is formed in an annular circular shape and a depressed portion for forming the film-forming resin solution in a cylindrical shape,

And a porous element through which the film-forming resin solution passes from the side is provided in the liquid storage part.

[2] A hollow fiber spinning nozzle according to [1], wherein the porous element has a three-dimensional mesh structure.

[3] The hollow fiber spinning nozzle according to [1] or [2], wherein the porous element is in the form of a cylinder.

[4] The hollow fiber spinning nozzle according to [3], wherein the cylindrical porous element is disposed such that the film-forming resin solution passes from the outer circumferential surface to the inner circumferential surface.

[5] The hollow fiber spinning nozzle according to any one of [1] to [4], wherein the porous element comprises a sintered body of fine metal particles.

[6] A method for producing a film-forming resin solution, which comprises: a liquid storage part for storing a solution in the form of an annular circular ring in a film-forming resin solution; and a hollow part having two or more resin flow paths having a depressed part for forming a film- It is a hollow fiber spinning nozzle that emits desert,

The hollow fiber spinning nozzle according to any one of [1] to [5], wherein the porous element is provided in each of two or more liquid storage portions.

Another aspect of the hollow fiber spinning nozzle of the present invention has the following configuration.

[7] A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer,

And a resin flow path for flowing a film-forming resin solution for forming the porous film layer inside,

Wherein the resin flow path has a liquid storage portion for storing the liquid in which the film-forming resin solution is formed in an annular circular shape and a depressed portion for forming the film-forming resin solution in a cylindrical shape,

Wherein the liquid storage portion is divided into two or more liquid storage chambers,

Wherein at least two supply passages for supplying the film-forming resin solution from the liquid storage chamber at the upper end to the liquid storage chamber below the liquid storage chamber are provided along the outer wall of the liquid storage portion.

Another aspect of the hollow fiber spinning nozzle of the present invention has the following configuration.

[8] A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer,

And a resin flow path for flowing a film-forming resin solution for forming the porous film layer inside,

Wherein the resin flow path has a liquid storage portion for storing the liquid in which the film-forming resin solution is formed in an annular circular shape and a depressed portion for forming the film-forming resin solution in a cylindrical shape,

Wherein a filling layer filled with particles is provided in the liquid storage portion.

Another aspect of the hollow fiber spinning nozzle of the present invention has the following configuration.

[9] A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer,

And a resin flow path for flowing a film-forming resin solution for forming the porous film layer inside,

Wherein the resin flow path has a liquid storage part for storing the solution in the form of an annular ring of the film-forming resin solution and a shaping part for shaping the film-forming resin solution into a cylindrical shape,

Wherein the liquid storage portion is divided into two or more stages on the upper and lower sides,

Wherein the upper liquid storage portion and the liquid storage portion immediately below the liquid storage portion are communicated by the resin supply portion.

(10), wherein the liquid storage portion is divided into three or more stages, a resin supply portion for connecting the n-th stage (n is a natural number) liquid storage portion and the (n + 1) th stage liquid storage portion, and the resin supply portion for communicating the (n + 2) -th liquid storage portion is disposed at a position shifted along the circumferential direction of the liquid storage portion.

[11] The hollow fiber spinning nozzle according to [9] or [10], wherein each of the resin supply portions is arranged in order from the upper end side in the circumferential direction of the liquid storage portion with respect to the central axis of the hollow portion.

Another aspect of the hollow fiber spinning nozzle of the present invention has the following configuration.

[12] A method for producing a porous film comprising a resin flow path for flowing a film-forming resin solution for forming the porous film layer,

Wherein the resin flow path has a solution reservoir for reserving the solution by making the membrane-forming resin solution into an annular circular shape and a depressed portion for forming the film-forming resin solution into a cylindrical shape, And a meandering portion for skewing the film-forming resin solution vertically while maintaining the film-forming resin solution in an annular circular shape.

Another aspect of the hollow fiber spinning nozzle of the present invention has the following configuration.

[13] A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer,

And a resin flow path for flowing a film-forming resin solution for forming the porous film layer inside,

Wherein the resin flow path has a solution reservoir for storing the solution of the film-forming resin solution in an annular circular shape and a depressed portion for shaping the film-forming resin solution into a cylindrical shape,

Forming resin solution in the liquid storage portion so as to extend from one wall surface in the liquid storage portion to the other wall surface, Spray nozzle.

That is, the present invention relates to the following.

(1) A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer and a support, wherein the nozzle has a resin flow passage for flowing a film-forming resin solution forming the porous membrane layer, A hollow fiber spinning nozzle having at least one of the following (a) to (c), wherein the hollow fiber membrane nozzle has a liquid reservoir for storing a liquid resin solution and a hollow part for shaping the film-forming resin solution into a cylindrical shape. (a) The resin flow path is disposed so that the film-forming resin solution branches and merges. (b) the resin flow path is disposed so as to delay the flow of the film-forming resin solution. (c) The liquid storage portion or the negative portion includes a branching and merging means of the film-forming resin solution.

(2) The hollow fiber spinning nozzle according to (1), wherein the liquid storage portion has an endless circular shape.

(3) The hollow fiber spinning nozzle according to (1) or (2), wherein the resin flow channel has at least two merging portions in which the film-forming resin solution joins.

(4) The liquid storage portion or the negative portion includes a branching and merging means of the film-forming resin solution, and the branching and merging means are provided in the liquid storage portion, The hollow fiber spinning nozzle according to any one of (1) to (3), wherein the hollow fiber membrane is a porous element through which the solution passes.

(5) The hollow fiber spinning nozzle according to any one of (1) to (4), wherein the porous element has a three-dimensional mesh structure.

(6) The hollow fiber spinning nozzle according to any one of (1) to (5), wherein the porous element is in a cylindrical shape.

(7) The hollow fiber spinning nozzle according to (4), wherein the cylindrical porous element is disposed such that the film-forming resin solution passes from the outer circumferential surface to the inner circumferential surface.

(8) The hollow fiber spinning nozzle according to any one of (1) to (5), wherein the porous element is in the form of a disk.

(9) The hollow fiber spinning nozzle according to any one of (1) to (8), wherein the porous element comprises a sintered body of metal.

(10) The hollow fiber spinning nozzle according to (9), wherein the porous element comprises a sintered body of metal fine particles or a sintered body of a wire mesh laminate.

(11) The hollow fiber spinning nozzle according to any one of (1) to (10), wherein the hollow fiber spinning nozzle has a circular support passage through which the support passes, and the support passage has a diameter of 95% to 200% A hollow fiber spinning nozzle according to any one of the preceding claims.

(12) The hollow fiber spinning nozzle according to any one of (1) to (11), wherein the support comprises a braid or knit braid.

(13) The hollow fiber spinning nozzle according to any one of (1) to (3), wherein the hollow fiber spinning nozzle has two or more liquid reservoirs for storing a liquid of the film-forming resin solution and two or more resin channels having a depressed part for forming a film- The hollow fiber spinning nozzle according to any one of (1) to (12), wherein the means is the porous element provided in each of the liquid storage portions.

(14) Calculation on a cyclic section of the hollow fiber membrane The hollow fiber spinning nozzle according to any one of (1) to (13), wherein the number of confluence is 50 or more.

(15) A method for producing a film-forming resin solution, comprising the steps of: (a) providing a film-forming resin solution having a discharge port through which the film-forming resin solution is discharged, (1) to (14), wherein the pressure loss of the film-forming resin solution after passing through the porous element reaches a discharge port.

(16) The resin flow path is arranged so that the film-forming resin solution branches and joins, and the resin flow path has a liquid storage portion divided into two or more stages of liquid storage chambers, The hollow fiber spinning nozzle according to any one of (1) to (3), wherein two or more supply passages for supplying the film-forming resin solution from the liquid storage chamber at the upper end to the liquid storage chamber below the liquid storage chamber are provided.

(17) The liquid storing portion or the forming portion includes a branching and merging means of the film-forming resin solution, and the branching and merging means is a means for dividing and merging the film- Wherein the hollow fiber spinning nozzle is a hollow fiber membrane spinning nozzle according to any one of (1) to (3).

(18) The resin flow path is arranged so that the film-forming resin solution branches and merges, and the resin flow path has a liquid reservoir portion divided into upper and lower ends in two or more stages, The hollow fiber spinning nozzle according to any one of (1) to (3), wherein the liquid storage portion is in communication with the resin supply portion.

(19) The liquid storage portion is divided into three or more stages, a resin supply portion for connecting the n-th stage (n is a natural number) liquid storage portion and the (n + 1) th stage liquid storage portion, (18), wherein the resin supplying portion for communicating the n + 2-stage liquid storage portion is disposed at a position shifted in the circumferential direction of the liquid storage portion.

The hollow fiber spinning nozzle according to (18) or (19), wherein the resin supply portions of the hollow fiber membranes (20) are arranged at regular angular intervals in the circumferential direction of the liquid storage portion with respect to the central axis of the hollow portion.

(21) The resin flow path is provided with a delay means for delaying the flow of the film-forming resin solution, and the retarding means is provided between the liquid storage portion and the shaping portion, The hollow fiber spinning nozzle according to any one of (1) to (3).

(22) The resin flow path is arranged so that the film-forming resin solution branches and merges, and the resin flow path is provided so as to extend from one wall surface in the liquid storage portion toward the other wall surface. (1) to (3), which regulates the circulation of the film-forming resin solution in the reservoir.

(23) A method for producing a hollow fiber membrane having a hollow porous membrane layer and a support, comprising the steps of spinning a hollow hollow fiber membrane from a film-forming resin solution, coagulating the hollow fiber membrane with the coagulating solution, Removing the solvent from the hollow fiber membranes, decomposing the additives in the hollow fiber membranes from which the solvent has been removed, washing the hollow fiber membranes, drying the hollow fiber membranes after washing, and winding the hollow fiber membranes after drying And that the hollow fiber membrane is spun from the film-forming resin solution by the hollow fiber membrane spinning nozzle according to any one of (1) to (22), wherein the hollow fiber membrane is spun from the film- Wherein the hollow fiber membrane comprises a hollow fiber membrane.

(24) The hollow fiber membrane according to any one of (23) to (24), wherein the hollow fiber membrane has an outer diameter d of not less than 0.5 mm and not more than 5.0 mm radiated by sputtering the hollow fiber membrane and a value d / dh obtained by dividing an outer diameter d of the hollow fiber membrane by an inner diameter dh Wherein the hollow fiber membrane is formed by a method comprising the steps of:

(25) The method for producing a hollow fiber membrane according to (23) or (24), wherein the calculated number of junctions in the annular section of the hollow fiber membrane radiated in the spinning of the hollow fiber membrane is 50 or more.

The hollow fiber spinning nozzle of the present invention can produce a hollow fiber membrane in which cracking along the axial direction is less likely to occur even when the spinning speed is increased.

1 is a plan view showing an example of a hollow fiber spinning nozzle according to a first embodiment of the present invention.
Fig. 2 is a cross-sectional view of the hollow fiber spinning nozzle of Fig. 1 taken along a line I-I '. Fig.
Fig. 3 is a cross-sectional view of the hollow fiber membrane spinning nozzle of Fig. 2 taken along the line II-II '.
4 is a cross-sectional view showing another example of the hollow fiber spinning nozzle according to the first embodiment of the present invention.
5 is a cross-sectional view showing another example of the hollow fiber spinning nozzle according to the first embodiment of the present invention.
6 is a plan view showing an example of a conventional hollow fiber spinning nozzle.
FIG. 7 is a cross-sectional view of the hollow fiber spinning nozzle of FIG. 6 cut along a straight line III-III '.
FIG. 8 is a cross-sectional view of the hollow fiber spinning nozzle of FIG. 7 cut along a line IV-IV '. FIG.
9 is a plan view showing an example of a hollow fiber spinning nozzle according to a second embodiment of the present invention.
10 is a cross-sectional view of the hollow fiber spinning nozzle of Fig. 9 taken along the line I-I '.
11 is a plan view of the second spinning nozzle of the hollow fiber spinning nozzle of FIG.
12 is a cross-sectional perspective view of the second nozzle of Fig.
13 is a cross-sectional view of the hollow fiber spinning nozzle of Fig. 10 cut along a line II-II '.
14 is a plan view showing another example of the second nozzle in the hollow fiber membrane spinning nozzle according to the second embodiment of the present invention.
15 is a cross-sectional perspective view showing another example of the second nozzle in the hollow fiber membrane spinning nozzle of the second embodiment of the present invention.
16 is a plan view showing an example of a hollow fiber spinning nozzle according to a third embodiment of the present invention.
17 is a cross-sectional view of the hollow fiber spinning nozzle of FIG. 16 taken along a line I-I '.
18 is a cross-sectional view of the hollow fiber spinning nozzle of Fig. 17 taken along line II-II '.
19 is a cross-sectional view showing another example of the hollow fiber spinning nozzle according to the third embodiment of the present invention.
Fig. 20 is a cross-sectional view of the hollow fiber spinning nozzle of Fig. 19 taken along line III-III '. Fig.
21 is a plan view showing an example of a hollow fiber spinning nozzle according to a fourth embodiment of the present invention.
Fig. 22 is a cross-sectional view of the hollow fiber membrane spinning nozzle of Fig. 21 taken along the line I-I 'in the vertical direction.
Fig. 23 is a cross-sectional view of the second nozzle portion of the hollow fiber membrane spinning nozzle of Fig. 21 cut in the horizontal direction. Fig.
FIG. 24 is a cross-sectional view of the hollow fiber membrane spinning nozzle of FIG. 21 taken along the line II-II 'in the vertical direction. FIG.
Fig. 25 is a cross-sectional view of the third nozzle portion of the hollow fiber membrane spinning nozzle of Fig. 21 cut in the horizontal direction. Fig.
Fig. 26 is a cross-sectional view of the hollow fiber membrane spinning nozzle of Fig. 21 cut in a vertical direction to a straight line III-III '. Fig.
Fig. 27 is a cross-sectional view of the fourth nozzle portion of the hollow fiber membrane spinning nozzle of Fig. 21 cut in the horizontal direction. Fig.
FIG. 28 is a cross-sectional view of the hollow fiber spinning nozzle of FIG. 21 taken along the line IV-IV 'in the vertical direction. FIG.
Fig. 29 is a cross-sectional view of the fifth nozzle portion of the hollow fiber membrane spinning nozzle of Fig. 21 cut in the horizontal direction. Fig.
30 is a plan view showing an example of a hollow fiber spinning nozzle according to a fifth embodiment of the present invention.
31 is a cross-sectional view of the hollow fiber membrane spinning nozzle of FIG. 30 taken along a line I-I '.
Fig. 32 is a cross-sectional view of the hollow fiber membrane spinning nozzle of Fig. 31 taken along line II-II '.
FIG. 33 is a cross-sectional view of the hollow fiber membrane spinning nozzle of FIG. 31 taken along line III-III '. FIG.
34 is an enlarged cross-sectional view of a part of the meandering portion of Fig. 31 enlarged.
35 is a cross-sectional view showing another example of the hollow fiber spinning nozzle according to the fifth embodiment of the present invention.
36 is a plan view showing an example of a hollow fiber spinning nozzle according to a sixth embodiment of the present invention.
37 is a cross-sectional view of the hollow fiber membrane spinning nozzle of Fig. 36 taken along a line I-I '.
38 is a cross-sectional view of the hollow fiber spinning nozzle of Fig. 37 taken along the line II-II '.
39 is a plan view of the second spinning nozzle in the hollow fiber spinning nozzle of Fig. 36. Fig.
40 is a plan view showing another embodiment of the liquid storage portion of the hollow fiber membrane spinning nozzle according to the sixth embodiment of the present invention.
41 is a plan view showing another example of the hollow fiber spinning nozzle according to the sixth embodiment of the present invention.
42 is a partial cross-sectional view of the hollow fiber membrane spinning nozzle of FIG. 41 cut along a line III-III '.
Fig. 43 is a cross-sectional view of the hollow fiber membrane spinning nozzle of Fig. 42 taken along the line IV-IV '. Fig.
44 is a plan view showing another example of the hollow fiber spinning nozzle according to the fifth embodiment of the present invention.

The hollow fiber spinning nozzle of the present invention is a spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer. The hollow fiber spinning nozzle of the present invention may be formed by spinning a hollow fiber membrane having a porous membrane layer on the outer side of a hollow support, or by spinning a hollow fiber membrane having a hollow porous membrane layer without a hollow support . It is also possible to spin the hollow fiber membrane having a single-layer porous membrane layer, or to spin a hollow fiber membrane having a multi-layer porous membrane layer.

It is also possible to spin a hollow fiber membrane having a porous film layer formed by one kind of film-forming resin solution, or to spin a hollow fiber membrane in which a porous membrane layer formed by another film-forming resin solution is laminated .

The method for producing a hollow fiber membrane according to the present invention is a method for producing a hollow fiber membrane having a hollow porous membrane layer including a hollow fiber membrane spun by the hollow fiber membrane spinning nozzle. The hollow fiber membrane produced by the spinning nozzle or the manufacturing method of the present invention has a hollow center.

The hollow support may be, for example, a hollow knit braid or a braid braided with various fibers. Further, various materials may be used singly or in combination. Examples of the fiber used in the hollow knit braid and the braid include synthetic fibers, semi-synthetic fibers, regenerated fibers, natural fibers and the like. The form of the fiber may be monofilament, multifilament, or spun yarn.

As the support, knitted braids of polyester multifilament are preferable from the viewpoints of tensile strength, flexibility, chemical resistance, and transmission inhibition.

The outer diameter of the support is preferably 0.3 to 4.8 mm, more preferably 1.0 to 3.0 mm, and further preferably 1.5 to 2.6 mm.

The support may be produced, for example, by using the support production apparatus described in the brochure WO 2009/142279. That is, the support manufacturing apparatus comprises a bobbin, a circular knitting machine for circularly cutting the yarn drawn out from the bobbin, a cord feeding device for tensioning the hollow knit braid knitted by the circular knitting machine with a predetermined tension, a heat kneading device for heating the hollow knit braid, And a take-up device for taking up the hollow-shaped knit braid heat-treated, and a take-up device for taking up the hollow knit braid on a bobbin as a support.

For the formation of the porous film layer, a film-forming resin solution is used. The film-forming resin solution used in the present invention is a solution (a film-forming solution) obtained by dissolving a film-forming resin and an additive (pore-forming agent) for the purpose of phase separation control in an organic solvent for both solvents.

As the film-forming resin, an ordinary resin used for forming a porous membrane layer of a hollow fiber membrane can be used. For example, a polysulfone resin, a polyethersulfone resin, a sulfonated polysulfone resin, a polyvinylidene fluoride resin, Rhenitrile resin, polyimide resin, polyamideimide resin, and polyesterimide resin. These resins can be appropriately selected and used according to their desirability, and polyvinylidene fluoride resins are preferred because of their excellent chemical resistance.

As the additive (pore-forming agent), for example, a hydrophilic polymer resin such as a monoole, diol, triol or polyvinylpyrrolidone represented by polyethylene glycol can be used. These can be appropriately selected and used according to the desire, and polyvinylpyrrolidone is preferable because of its excellent thickening effect.

The organic solvent is not particularly limited as long as it can dissolve all of the film-forming resin and additive (s) described above, and examples thereof include dimethylsulfoxide, N-methyl-2-pyrrolidone, dimethylacetamide, Or dimethylformamide can be used.

Any other additives other than the pore-forming agent, water or the like may be used as the optional ingredient within the range of the film-forming stock solution used herein, as long as the control of phase separation is not inhibited.

The spinning nozzle of the present invention has a resin flow path for flowing a film-forming resin solution for forming a porous film layer, the resin flow path including a liquid storage portion for storing the film-forming resin solution, Wherein at least the resin flow path is disposed so that the film-forming resin solution branches and merges, or the resin flow path is provided with a delay for delaying the flow of the film-forming resin solution into the resin flow path, Or the liquid storage portion or the forming portion is provided with means for branching and merging the film-forming resin solution. The spinning nozzle of the present invention has the above-described structure and has a function of making the film-forming resin solution uniform in the spinning nozzle of the present invention.

Since the resin flow path of the spinning nozzle of the present invention is arranged so that the film-forming resin solution branches and joins, or the resin flow path has the branching and merging means, the film forming resin solution flowing through the resin flow path The molten resin solution branches, and the branched film-forming resin solution merges. It is preferable that the resin flow path has a merging portion in which the branched film-forming resin solution merges and has at least two merging portions. By having the resin flow path having two or more confluent portions, the film-forming resin is entirely uniform in the spinning nozzle of the present invention.

The branching and merging means may be a porous element through which the film-forming resin solution is installed, provided in the liquid storage portion, or may be a filling layer in which particles are filled in the liquid storage portion.

The resin flow path arranged so that the film-forming resin solution branches and merges has a liquid reservoir divided into two or more liquid reservoirs, and the liquid reservoir from the upper liquid reservoir to the liquid reservoir under the liquid reservoir Or may have two or more supply paths for supplying the film-forming resin solution. The resin flow path may have a liquid reservoir portion divided into two or more stages in the upper and lower portions, and the liquid reservoir portion at the upper end and the liquid reservoir portion immediately below the liquid reservoir portion may be communicated with each other by the resin supply portion. The resin flow path has a dam which regulates the circulation of the film-forming resin solution in the liquid storage portion so as to extend from one wall surface in the liquid storage portion toward the other wall surface do.

By having the spinning nozzle of the present invention as described above, the film-forming resin solution flowing through the resin flow path branches and merges, and the film-forming resin solution is homogenized in the spinning nozzle of the present invention , It is suppressed that the starting point of the crack along the axial direction is formed in the porous film layer formed by the film-forming resin solution.

The resin flow path of the spinning nozzle of the present invention may be provided with a delay means for delaying the flow of the film-forming resin solution, and the retarding means may be provided between the liquid storage portion and the shaping portion, A meandering may be performed in which the upper and lower portions are skewed while being maintained in a circular shape.

By having the spinning nozzle of the present invention as described above, the time for which the film-forming resin solution flowing through the resin flow path stays in the nozzle becomes longer, and the film- The inside of the porous film layer is uniformized and the starting point of the crack along the axial direction is suppressed from being formed in the porous film layer formed by the film-forming resin solution.

In the spinning nozzle of the present invention, it is considered that the film-forming resin solution is microscopically stirred as a whole by having the above-mentioned structure, whereby entanglement of the film-forming resins is released. As a result, the film-forming resin solution that has passed through the hollow fiber spinning nozzle of the present invention becomes entangled not only with the joining portion but also with the film-forming resin as a whole, And is uniformed inside the spinning nozzle. It is considered that the hollow fiber membrane produced by the homogenized film-forming resin solution is prevented from having a starting point of a crack along the axial direction because the stress concentration point is dispersed when a load such as flatness is generated.

Hereinafter, an embodiment of the hollow fiber spinning nozzle according to the first embodiment of the present invention is shown and described in detail. Figs. 1 to 3 are schematic views showing a hollow fiber membrane spinning nozzle 11 (hereinafter referred to as " spinning nozzle 11 ") which is an example of an embodiment of the hollow fiber membrane spinning nozzle according to the first embodiment of the present invention. The spinning nozzle 11 is a spinning nozzle for producing a hollow fiber membrane in which 12 layers of porous film layers are laminated on the outside of a hollow support. Hereinafter, the inner porous film layer in the hollow fiber membrane produced by the spinning nozzle 11 is referred to as a first porous film layer, and the outer porous film layer is referred to as a second porous film layer.

The spinning nozzle 11 of the present embodiment has a first nozzle 111, a second nozzle 112 and a third nozzle 113 as shown in Figs.

As shown in Fig. 2, the spinning nozzle 11 is provided with a support passage 114 through which a hollow support is passed, a resin passage 114 through which the first film-forming resin solution for forming the first porous film layer flows, And a resin flow path 116 for flowing the first film-forming resin solution forming the second porous film layer.

As shown in Figs. 2 and 3, the resin flow path 115 is provided with an introducing portion 117 through which the first film-forming resin solution is introduced into the first nozzle 111 and the second nozzle 112, The first film-forming resin solution has a first liquid storage portion 118 for storing a solution in the form of an annular circular ring, and a first portion 119 for shaping the first film-forming resin solution into a cylindrical shape. The resin flow path 116 includes an inlet 120 through which the second film-forming resin solution is introduced, a second solution storage 121 through which the second film-forming resin solution is circulated in an annular circular shape, And a second negative portion 122 for forming the second film-forming resin solution into a cylindrical shape. Further, in this example, the composite part 123 is formed by the second and the third cylindrical parts 122 and 119. That is, the second film-forming resin solution is formed into a cylindrical shape in the second bulge portion 122 and the second film-forming resin solution is applied to the first film formation So that it is laminated and compounded on the outside of the resin solution.

The support passage 114, the first liquid reservoir 118, the first reservoir 119, the second reservoir 121, the second reservoir 122, and the complex part 123 have center axes It is consistent.

The spinning nozzle 11 is divided into branching and merging means, that is, a first film-forming resin solution and a second film-forming portion, respectively, in the interior of the first liquid storage portion 118 and the interior of the second liquid storage portion 121 And porous resin elements 131 and 132 through which the resin solution flows from the outer circumferential surface toward the inner circumferential surface, respectively.

The porous element 131 or 132 is a branching and joining means for branching and joining the film-forming resin solution flowing through the resin flow path. The porous element 131 or 132 passes through the porous element 131 or 132, Is uniformed inside the spinning nozzle of the present invention.

The spinning nozzle 11 is configured such that the hollow support is supplied from the support supply port 114a and is led out from the support outlet 114b and the first film-forming resin solution and the second film- Is supplied from the supply port 115a or 116a, and is discharged in the form of a cylinder around the support from the discharge port 123a in a state of being combined into two layers.

Figs. 9 to 13 are schematic views showing a hollow fiber membrane spinning nozzle 21 (hereinafter referred to as " spinning nozzle 21 ") which is an example of an embodiment of the hollow fiber membrane spinning nozzle according to the second embodiment of the present invention. The spinning nozzle 21 is a spinning nozzle for producing a hollow fiber membrane in which one layer of a porous film layer is laminated on the outside of a hollow support body.

The spinning nozzle 21 of the present embodiment has a first nozzle 211, a second nozzle 212, and a third nozzle 213 as shown in Figs. 9 and 10.

As shown in Fig. 10, the spinning nozzle 21 has a support passage 214 through which a hollow support is passed, and a resin passage 215 through which a film-forming resin solution for forming a porous film layer flows I have. The resin flow path 215 includes an inlet portion 216 into which the film-forming resin solution is introduced, a liquid storage portion 217 which stores the solution in the form of an annular circular cylinder in the form of an annular circular cylinder, And a negative portion 218 which is formed as a hollow portion. The liquid storage portion 217 is divided into two stages, that is, a first liquid storage chamber 217A in the portion of the second nozzle 212 and a second liquid storage chamber 217B in the portion of the third nozzle 213. [ The support shaft 214, the first liquid reservoir 217A, the second liquid reservoir 217B, and the annular portion 218 have their center axes aligned with each other.

The spinning nozzle 21 is configured such that the hollow support is supplied from the support supply port 214a and is led out from the support outlet 214b and the film forming resin solution is supplied from the resin supply port 215a, And is discharged in a cylindrical shape from the support portion 215b to the periphery of the support.

That is, the resin flow path 215 of the present embodiment is arranged so that the film-forming resin solution branches and merges by having the solution reservoir 217 or the above-mentioned tubular portion 218. Therefore, the film-forming resin solution passes through the resin flow path 215 and becomes uniform in the spinning nozzle of the present invention.

16 to 18 are schematic views showing a hollow fiber membrane spinning nozzle 31 (hereinafter referred to as " spinning nozzle 31 ") which is an example of an embodiment of the hollow fiber membrane spinning nozzle according to the third embodiment of the present invention. The spinning nozzle 31 is a spinning nozzle for producing a hollow fiber membrane in which one layer of a porous film layer is laminated on the outside of a hollow support.

The spinning nozzle 31 of the present embodiment has a first nozzle 311 and a second nozzle 312 as shown in Figs. 16 and 17. Fig.

As shown in Fig. 17, the spinning nozzle 31 is provided with a support passage 313 for allowing a hollow support to pass therethrough and a resin passage 314 for flowing a film-forming resin solution for forming a porous film layer I have. The resin flow path 314 includes an introduction portion 315 into which the film-forming resin solution is introduced, a liquid storage portion 316 in which the film-forming resin solution is formed into an annular circular shape, and a liquid storage portion 316, And has a hollow portion 317 which is formed as a hollow portion. In the liquid storage portion 316, a filling layer 320 filled with the branching and merging means, that is, the particles 321, is provided. The support shaft 313, the liquid reservoir 316, and the tubular portion 317 have their central axes aligned with each other.

The spinning nozzle 31 is configured such that the hollow support is fed from the support feed port 313a and is led out from the support outlet 313b and the film forming resin solution is fed from the resin feed port 314a, (314b) to the periphery of the support body in a cylindrical shape.

The filling layer 320 passes through the filling layer 320 as branching and joining means for branching and merging the film-forming resin solution flowing through the resin flow path, And is uniformed inside the spinning nozzle.

21 to 29 are schematic views showing a hollow fiber membrane spinning nozzle 41 (hereinafter referred to as " spinning nozzle 41 ") which is an example of an embodiment of the hollow fiber membrane spinning nozzle according to the fourth embodiment of the present invention. The spinning nozzle 41 is a spinning nozzle for producing a hollow fiber membrane in which one type of porous film layer is laminated on the outside of a hollow support.

21 to 29, the spinning nozzle 41 of this embodiment has a first nozzle 411, a second nozzle 412a, a third nozzle 412b, a fourth nozzle 412c and a fifth nozzle 412d. The spinning nozzle 41 has a support passage 413 for allowing a hollow support to pass therethrough and a resin flow passage 414 for flowing a film-forming resin solution for forming a porous film layer.

The support passage 413 passes through the central portion of the spinning nozzle 41.

As shown in Figs. 22 to 24, the resin flow path 414 has an inlet 415 for introducing a film-forming resin solution into a portion of the first nozzle 411 and a portion of the second nozzle 412a, A first liquid reservoir 416A for circulating the liquid resin solution in the form of a ring, a first liquid reservoir 417A for shaping the film-forming resin solution into a cylindrical shape, and a first resin supply unit 416a have. 25 and 26, the resin flow path 414 is provided with a second liquid storage portion 416B for storing liquid by forming a film-forming resin solution in an annular shape on the portion of the third nozzle 412b, A second negative portion 417B for forming the film-forming resin solution into a cylindrical shape, and a second resin supply portion 416b. 27 and 28, the resin flow path 414 is provided with a third liquid storage portion 416C for storing liquid by forming a film-forming resin solution in a ring shape on the portion of the fourth nozzle 412c, A third section 417C for shaping the film-forming resin solution into a cylindrical shape, and a third resin supply section 416c. 22 and 29, the resin flow path 414 is provided with a fourth liquid storage portion 416D for storing liquid by forming a film-forming resin solution in an annular shape on the portion of the fifth nozzle 412d, And a fourth sub-section 417D for shaping the film-forming resin solution into a cylindrical shape.

As described above, the liquid storage portion 416 is provided at the upper and lower portions of the first liquid storage portion 416A, the second liquid storage portion 416B, the third liquid storage portion 416C, the fourth liquid storage portion 416D And the first liquid reservoir 416A communicates with the second liquid reservoir 416B in the first resin supply portion 416a and the second liquid reservoir 416B communicates with the second resin reservoir 416b in the second resin reservoir 416b, And the third liquid reservoir 416C communicates with the fourth liquid reservoir 416D in the third resin supply portion 416c.

Further, in this example, the composite portion 417 is formed by the first to fourth annular portions 417A to 417D. In other words, after the first section 417A, the film-forming resin solution is formed into a cylindrical shape in each of the negative sections, and at the same time, on the outer side of the film-forming resin solution flowing through the upper section, And a film-forming resin solution are successively laminated.

A second liquid reservoir 416B and a third liquid reservoir 416C and a fourth liquid reservoir 416D and a first liquid reservoir 417A ), The second bulb portion 417B, the third bulb portion 417C, and the fourth bulb portion 417D have their central axes aligned with each other.

The spinning nozzle 41 is configured such that the hollow support is supplied from the support supply port 413a and is led out from the support outlet 413b and the film forming resin solution is supplied from the resin supply port 414a, (414b) to the periphery of the support body in a cylindrical shape.

That is, the resin flow path 414 of the present embodiment has the resin reservoir 416A, 416B, 416C or 416D, the resin supply portion 416a, 416b or 416c, the depressions 417A, 417B, 417C or 417D, Or the composite portion 417 so that the film-forming resin solution is branched and merged. Therefore, the film-forming resin solution passes through the resin flow path 414 and becomes uniform in the spinning nozzle of the present invention.

30 to 34 are schematic views showing a hollow fiber spinning nozzle 51 (hereinafter referred to as " spinning nozzle 51 ") which is an example of an embodiment of the hollow fiber spinning nozzle according to the fifth embodiment of the present invention. The spinning nozzle 51 is a spinning nozzle for producing a hollow fiber membrane in which a porous film layer of one layer is laminated on the outside of a hollow support body.

The spinning nozzle 51 of the present embodiment has a first nozzle 511 and a second nozzle 512 as shown in Figs. 30 and 31. Fig.

As shown in Fig. 31, the spinning nozzle 51 is provided with a support passage 513 for passing a hollow support member and a resin passage 514 for flowing a film-forming resin solution for forming a porous film layer I have. The resin flow path 514 includes an introduction portion 515 into which the film-forming resin solution is introduced, a liquid storage portion 516 that stores the solution in the form of an annular circular ring in the form of a film-forming resin solution, And the like. The spinning nozzle 51 also has a meandering portion 518 between the liquid storage portion 516 and the negative portion 517 for vertically skewing the film-forming resin solution while keeping it in an annular circular shape. The support passage 513, the liquid storage portion 516, the meandering portion 518 and the tabular portion 517 have their central axes aligned with each other.

When the hollow fiber membrane is formed, one type of film-forming resin solution may be used alone, or a plurality of film-forming resin solutions may be used. For example, in the case of using two kinds of film-forming resin solutions, it is possible to laminate composite films so as to cover one film-forming resin solution so that a cylindrical layer of a ring- . The cylindrical layer on the side of the cylindrical cross section of the hollow fiber membrane near the center axis is called an inner layer and the layer on the outer surface side is called an outer layer.

The spinning nozzle 51 is configured such that the hollow support is supplied from the support supply port 513a and is led out from the support outlet 513b and the film forming resin solution is supplied from the resin supply port 514a, 514b to the periphery of the support body in a cylindrical shape.

That is, the resin flow path 514 of the present embodiment is disposed so as to delay the flow of the film-forming resin solution by having the meandering portion 518 as the retarding means. Therefore, the film-forming resin solution passes through the resin flow path 514 and becomes uniform in the spinning nozzle of the present invention.

The longer the residence time (residence time) of the film-forming resin solution in the meandering portion is, the more the effect is exhibited. The residence time is preferably 1 second to 5 minutes, more preferably 1 minute to 3 minutes.

Hereinafter, an embodiment of the hollow fiber spinning nozzle according to the sixth embodiment of the present invention will be described in detail.

[First Embodiment]

36 to 39 are schematic views showing a hollow fiber membrane spinning nozzle 61 (hereinafter referred to as " spinning nozzle 61 ") which is an example of an embodiment of the hollow fiber membrane spinning nozzle according to the sixth embodiment of the present invention. The spinning nozzle 61 is a spinning nozzle for producing a hollow fiber membrane having a porous film layer formed on the outer side of a hollow support.

The spinning nozzle 61 of this embodiment has a first nozzle 611 and a second nozzle 612 as shown in Figs.

As shown in Fig. 37, the spinning nozzle 61 is provided with a support passage 613 for allowing a hollow support to pass therethrough and a resin passage 614 for flowing a film-forming resin solution for forming a porous film layer I have. 37 to 39, the resin flow path 614 includes an inlet portion 615 into which a film-forming resin solution is introduced, and a branching and joining means, that is, a film-forming resin solution, And a negative portion 617 for forming a film-forming resin solution stored in an annular ring shape in an annular ring shape in the liquid storage portion 616 in a concentric cylindrical form with the support passage 613. The liquid storage portion 616 includes a liquid storage portion 616,

The spinning nozzle 61 is configured such that the hollow support is supplied from the support supply port 613a and is led out from the support outlet 613b and the film forming resin solution flows from the resin supply port 614a to the resin flow path 614 The liquid is stored in the liquid reservoir 616 and discharged from the discharge port 614b to the periphery of the supporter in a cylindrical shape after being formed in the tab 617. [

That is, the resin flow path 614 of the present embodiment has the liquid storage portion 616 or the negative portion 617, so that the film-forming resin solution is branched and merged. Therefore, the film-forming resin solution passes through the resin flow path 614 and becomes uniform in the spinning nozzle of the present invention.

The second nozzle 112, 212, 312, 412a, 512 and 612, the third nozzle 113, 213, 412b, the fourth nozzle 412c And the fifth nozzle 412d may be those commonly used as spinning nozzles for hollow fiber membranes, and stainless steel (SUS) is preferable from the viewpoints of heat resistance, corrosion resistance, strength, and the like.

The cross-sectional shape of the support passages 114, 214, 313, 413, 513, and 613 is preferably circular. However, the cross-sectional shapes of the support passages 114, 214, 313, 413, 513, and 613 are not limited to circular shapes.

The inner diameter (diameter) of the support passages 114, 214, 313, 413, 513 and 613 may be appropriately set in accordance with the diameter of the hollow support member to be used. For example, the outer diameter of the support member may be about 0.3 mm to 4.8 mm , The diameter of the support passage is preferably 95% to 200%, more preferably 100% to 150%, and even more preferably 105% to 120% with respect to the outer diameter of the support.

If the diameter of the support passage is excessively smaller than the outer diameter of the support, the resistance at the time of running of the support becomes large and the running fluctuation occurs, and the film thickness becomes uneven or the defect portion becomes easy to form. If the diameter of the support passage is excessively large, the supporting position of the support in the support passage is largely eccentric and the contact position in the circumferential direction of the film-forming resin solution and the support is displaced, There is a possibility of occurrence.

Sectional shapes of the inlet portions 117, 216, 315, 415, 515 and 615 of the resin flow paths 115, 215, 314, 414, 514 and 614 and the inlet portion 120 of the resin flow paths 116 are, A circular shape is preferable. However, the sectional shapes of the introducing portions 117, 216, 315, 415, 515, and 615 and the introducing portion 120 are not limited to circular shapes.

The diameters of the inlet portions 117, 216, 315, 415, 515, and 615 and the inlet portion 120 are not particularly limited.

The first liquid storage portion 118 of the first embodiment of the present invention is a portion for storing liquid by making the first film-forming resin solution circulating the introduction portion 117 into an endless circular shape. The first liquid storage portion 118 is preferably circular in cross section as in this example. However, the cross-sectional shape of the first liquid storage portion 118 is not limited to the circular cross-section.

The cross-sectional shape of the first liquid storage portion 118 is an annular shape as shown in Fig. 3, and the center of the first liquid storage portion 118 and the center of the support passage 114 coincide with each other. In the first liquid storage portion 118, the first film-forming resin solution flows from the inlet portion 117 side to the both side in an arcuate shape so as to join in the joining portion 118a on the opposite side of the inlet portion 117 .

2, a slit portion 118b may be formed in the vicinity of the first cylindrical portion 119 in the first liquid storage portion 118. [ Particularly, when the film-forming resin solution passes through the outer peripheral surface of the porous element 131, which will be described later, from the outer peripheral surface to the inner peripheral surface, if the discharge uniformity in the circumferential direction does not become a desired level, It is preferable from the viewpoint of improving the uniformity of discharge in the circumferential direction.

In this example, the porous element 131 through which the film-forming resin solution passes from the side is provided in the first liquid storage part 118. The porous element 131 of this example has a cylindrical shape and the first film-forming resin solution supplied into the first liquid storage portion 118 passes from the outer peripheral surface of the porous element 131 to the inner peripheral surface.

As the porous element 131, a film-forming resin solution having fine holes passing from the outer circumferential surface to the inner circumferential surface can be used. For example, a filter for filtering the film-forming resin solution can be used. The porous element 131 is preferably a sintered body of metal fine particles from the viewpoints of strength, thermal conductivity, chemical resistance, and structural uniformity. However, the porous element 131 is not limited to a sintered body of metal fine particles, but may be a sintered body of metal fibers, a laminate of metal mesh, a sintered laminate (sintered body of a wire net laminate), a ceramic porous body, Or a filler of metal fine particles.

By providing the porous element 131 in the spinning nozzle 11, it is possible to suppress the formation of a starting point of a crack along the axial direction in the first porous film layer formed by the first film-forming resin solution. The reason why the above effect can be obtained by the porous element 131 is not clear, but it is considered as follows.

In the conventional spinning nozzle 1101 shown in Figs. 6 to 8, when the spinning speed is increased, the starting point of the crack along the axial direction formed in the porous film layer is divided into two parts in the liquid storage part 1116 Is formed at a position corresponding to the confluence portion 1116a where the true film-forming resin solution joins. In this joining portion 1116a, the entanglement of the film-forming resin tends to be smaller than the portion other than the joining portion 1116a, and this becomes a stress concentration point when a load such as flatness is generated in the hollow fiber membrane, It is considered that a starting point of a crack along the boundary line is formed. On the other hand, in the spinning nozzle 11, all the first film-forming resin solution supplied into the first liquid storage portion 118 passes through the porous element 131 from the outer peripheral surface toward the inner peripheral surface. At this time, it is considered that the first film-forming resin solution is entirely microscopically stirred, and entanglement of the film-forming resins is released. As a result, the first film-forming resin solution passed through the inside of the porous element 131 becomes entangled not only with the joining portion 118a but also with the film-forming resin as a whole, , It is considered that the uniformity in the spinning nozzle of the present invention is suppressed and the starting point of the crack along the axial direction is suppressed by dispersing the stress at the time of generation of load such as flatness in the hollow fiber membrane.

The porous element 131 is preferably a porous body having a three-dimensional mesh structure, since it is easy to obtain a hollow fiber membrane which is less prone to cracking. A porous body having a three-dimensional mesh structure means that the film-forming resin solution does not flow linearly when passing through the inside of the porous element from the outer peripheral surface toward the inner peripheral surface, but passes through the inner peripheral surface while moving in the vertical direction or the peripheral direction. Dimensional porous structure. By using a porous body having a three-dimensional mesh structure as the porous element 131, the first film-forming resin solution is repeatedly finely branched and merged as a whole to be uniform in the spinning nozzle of the present invention, It is considered that a starting point of a crack along the axial direction is hardly formed in the porous film layer even when the speed is increased. Further, in the porous element having the same pore diameter and the same thickness, the pressure loss is also advantageous. It is also preferable from the viewpoints of alien substance in the first film-forming resin solution and gelation.

As the porous element having a three-dimensional mesh structure, there can be mentioned a porous element of a fiber-winding structure, or a porous element of a structure obtained by laminating a resin, a metal fine particle or a wire net, and sintering the same.

The shape of the porous element 131 may be a disc shape or a cylindrical shape, but the shape is not particularly limited. It is preferable that the first film-forming resin solution supplied into the first liquid storage portion 118 flows from the upper surface to the lower surface of the porous element or flows from the outer peripheral surface to the inner peripheral surface of the porous element, It is more preferable that the first film-forming resin solution supplied into the one-liquid storage portion 118 flows from the outer peripheral surface to the inner peripheral surface of the porous element. It is more preferable that the first film-forming resin solution flows annularly from the outer peripheral surface to the inner peripheral surface of the porous element.

In particular, as for the shape of the porous element 131, it is easy to increase the area through which the first film-forming resin solution passes without changing the size of the hollow fiber membrane spinning nozzle in the radial direction, From the viewpoint of facilitating the speed-up, it is preferable to have a cylindrical shape as in this example.

As the shape of the porous element 131, it is preferable that the cylindrical shape is cylindrical as compared with the disk shape, and the cylindrical shape is preferable from the viewpoint of pressure resistance.

Further, it is preferable that the porous element 131 is free of joints such as a cylindrical candle filter, which is a typical candle filter, and which is formed by winding a flat element into a cylindrical shape and welding the joint. However, the present invention is not limited thereto.

By using such a porous element having no joint, it is easy to make the passing property of the first film-forming resin solution uniform. Examples of the structure of such a seamless porous element include a cylindrical fiber winding structure, an etching machining structure of a metal tube, a laser hole machining structure of a metal tube, a cubic honeycomb structure, a structure having two or more fine holes communicating the outer periphery and the inner periphery Or more of the donut-shaped original plates are integrally laminated in a concentric circular shape, or a structure in which resin or metal fine particles are sintered and integrated into a cylindrical shape.

In the spinning nozzle 11, the pressure loss when the supplied first film-forming resin solution passes through the porous element 131 is lower than the pressure until the first film-forming resin solution reaches the porous element 131 Is preferably larger than the pressure and pressure loss from the time when the first film-forming resin solution passes through the porous element 131 until reaching the discharge port 123a. If the pressure loss when the first film-forming resin solution passes through the porous element 131 is set as described above, the flow of the first film-forming resin solution inside the first liquid storage part 118 is reduced A flow in which the outer side of the element 131 is moved along the circumferential direction and is filled and then the porous element 131 is passed through the inner circumferential surface as a whole becomes the flow with the least energy loss. As a result, the flow of the first film-forming resin solution when passing through the porous element 131 is consequently easily made uniform in the circumferential direction in the spinning nozzle of the present invention, The uniformity of the thickness becomes easy.

Concretely, in the slit portion 118b, the first and second cylindrical portions 119 and 122, the pressure loss is not generated as much as possible (the gap is enlarged) It is preferable to provide a passage resistance so that the uniformized state of the first film-forming resin solution that has passed through the porous element 131 is easily maintained to the discharge port 123a.

The pressure loss when the first film-forming resin solution passes through the porous element 131 can be controlled by adjusting the structure of the porous element 131, the hole diameter, or the like.

The pore diameter of the porous element is preferably 1 to 200 占 퐉, more preferably 50 to 150 占 퐉, and even more preferably 70 to 120 占 퐉. The filtration accuracy is treated here as a pore diameter.

The first mold 119 is a portion formed in a cylindrical shape concentric with the support for passing the first film-forming resin solution in the first solution reservoir 118 through the support passage 114.

The width (distance between the inner wall and the outer wall) of the first cylindrical portion 119 can be appropriately set in accordance with the thickness of the first porous film layer to be formed.

The second liquid storage part 121 is a part for storing liquid by making the second film-forming resin solution circulating in the introduction part 120 into an annular circular shape. The second liquid storage part 121 is preferably circular in cross section as in this example. However, the cross-sectional shape of the second liquid storage part 121 is not limited to the circular cross section.

The sectional shape of the second liquid storage part 121 is circular like the first liquid storage part 118 and the center of the second liquid storage part 121 and the center of the support passage 114 coincide with each other. In the second liquid storage part 121, the second film-forming resin solution flows in an arc shape on both sides from the side of the introduction part 120, and flows in a circular arc shape in the joining part 121a on the opposite side of the introduction part 120, .

2, a slit portion 121b may be formed in the vicinity of the second cylindrical portion 122 in the second liquid storage portion 121. As shown in Fig. Particularly, when the film-forming resin solution passes through the outer side surface of the porous element 132, which will be described later, toward the inner side, if the discharge uniformity in the circumferential direction does not become a desired level, It is preferable to provide a resistance from the viewpoint of improving the uniformity of discharge in the circumferential direction.

In this example, the porous element 132 through which the film-forming resin solution passes from the side is provided in the second liquid storage part 121. [ The porous element 132 of this example is in the shape of a cylinder, and the second film-forming resin solution supplied into the second liquid storage part 121 passes through the inside from the outer peripheral surface toward the inner peripheral surface. The porous element 132 may be the same as the porous element 131 described above, and the preferred embodiment is also the same. By providing the porous element 132, it is possible to suppress the formation of a starting point of a crack along the axial direction in the second porous film layer formed by the second film-forming resin solution.

In addition, the pressure loss when the supplied second film-forming resin solution passes through the porous element 132 is the pressure loss until the second film-forming resin solution reaches the porous element 132, Is preferably larger than the pressure and pressure loss from when the forming resin solution passes through the porous element 132 until reaching the discharge port 123a. As a result, the flow of the second film-forming resin solution when passing through the porous element 132 is consequently easily made uniform in the circumferential direction within the spinning nozzle of the present invention, and the thickness of the formed second porous film layer It becomes easy to equalize.

The hollow fiber spinning nozzle of the present invention is characterized in that, in the case of a spinning nozzle for producing a hollow fiber membrane having two or more porous membrane layers like the spinning nozzle 11, two or more It is preferable to provide the branching and merging means, that is, the porous element, respectively in the liquid storage portion. When the starting point of the crack along the axial direction is formed in the inner porous film layer, the same portion of the outer porous film layer is liable to be cracked due to the influence of the starting point of the crack. By providing the porous element in each liquid storage portion like the spinning nozzle 11, it becomes easy to produce a hollow fiber membrane which is suppressed from occurrence of crack origin and is hard to be cracked.

The second annular portion 122 is a portion formed by concentrating the second film-forming resin solution in the second liquid storage portion 121 in a concentric circular cylindrical shape with a support through which the support film 114 passes. Further, in this example, the composite portion 123 is formed by the first and second cylindrical portions 119 and 122. In other words, the second film-forming resin solution which is cylindrical in shape in the second cylindrical portion 122 is simultaneously formed with a concentric circle on the outer side of the first film-forming resin solution flowing through the first cylindrical portion 119 So as to be laminated and composite. In the composite portion 123, by laminating and compositing each of the film-forming resin solutions in the nozzle, the bonding strength of each formed porous film layer is improved as compared with the case where they are laminated and mixed outside the nozzle. Further, it is advantageous in terms of simplification of nozzle structure and simplification of processing. Further, even if the respective film-forming resin solutions are laminated and combined in the composite portion 123, there is almost no adverse effect on the structure of each porous film layer due to the mutual solvent diffusion in these solutions.

The width of the composite portion 123 (distance between the inner wall and the outer wall) can be appropriately set in accordance with the thickness of the second porous film layer to be formed.

In the case of a nozzle for spinning hollow fiber membranes having two or more porous membrane layers, the hollow fiber membrane spinning nozzle of the present invention is characterized in that on the downstream side of the porous element inside the nozzle, It is preferable to have a complex part for laminating the solution in a concentric circular shape.

In the spinning of the hollow fiber membrane by the spinning nozzle 11, the hollow support is supplied from the support supply port 114a to the support passage 114, and the first film formation The resin resin solution and the second film-forming resin solution are supplied from the resin supply ports 115a and 116a to the resin flow paths 115 and 116, respectively. The first film forming resin solution flows into the first liquid storage part 118 from the introduction part 117 and branches outwardly of the porous element 131 in the first liquid storage part 118 to form an arc shape And the porous element 131 flows from the outer circumferential surface toward the inner circumferential surface and flows into the first tubular portion 119. [ In the first mold 119, the first film-forming resin solution is formed into a cylindrical shape. The second film-forming resin solution flows into the second liquid storage part 121 from the introduction part 120 and branches outward from the porous element 132 in the second liquid storage part 121 to form an arc shape And the porous element 132 flows from the outer circumferential surface toward the inner circumferential surface and flows into the second tubular portion 122. [ In the second mold 122, the second film-forming resin solution is formed into a cylindrical shape. In this example, since the composite portion 123 is formed in the first and second cylindrical portions 119 and 122, the second film-forming resin solution is formed into a cylindrical shape, Is laminated and compounded in the form of a concentric circle outside the first film-forming resin solution flowing through the first film-forming resin layer 119. The first film-forming resin solution and the second film-forming resin solution are discharged from the discharge port 123a in a state of being laminated and compounded in a concentric circle form, and at the same time, on the outer side of the support member led out from the support outlet 114b .

Thereafter, for example, in a container for bringing a film containing a water-containing gas into contact with the film-forming resin solution, the film-forming resin solution is allowed to pass through a coagulation bath in which the film-forming resin solution is brought into contact with the coagulating solution, , Or drying or the like to obtain a hollow fiber membrane.

The spinning nozzle of the present embodiment can spin a hollow fiber membrane having a calculated cross-sectional area of 50 or more.

The film-forming resin solution flowing through the nozzle branches and joins by passing through the porous element provided inside the liquid storage portion, and is formed into a cylindrical shape and discharged from the discharge port. Thereafter, the discharged film-forming resin solution is solidified and washed or dried to obtain a hollow fiber membrane. The above-mentioned calculation joining means means that, while the film-forming resin solution passes through the flow path in the nozzle, the resin solution is branched into a plurality of branched flow paths to flow, and at the outlet of the plurality of branched flow paths, And the number of holes at the flow outlet of the porous element. For example, when there are 100 holes on the side where the film-forming resin solution comes out of the cylindrical porous article, and the resin solution is discharged from the discharge port of one nozzle, the above-mentioned calculated merging number becomes 100.

It is considered that the nozzle, which is a three-dimensional structure, has a complicated flow path in the flow direction and many branching and joining are repeated. Actually, the number of joining is larger than the number of holes in the flow outlet. We think that it is the sum of the calculation to the minimum value.

When the number of the calculated joins is reduced, cracks tend to occur along the axial direction when a physical load is applied to the hollow fiber membrane, and cracks are less likely to occur as the number of calculated joins increases. A preferable range of the number of the above-described calculation is 50 to 3000, more preferably 200 to 2500, and most preferably 500 to 2000.

In the case where the number of holes of the porous element is unclear, for example, the total area of the holes is obtained from the product of the hollow ratio of the porous element and the filtration area, and this value is divided by the area per one hole The value is the number of holes. The hollow ratio means the percentage of the openings through which the film-forming resin solution can flow among the surfaces of the secondary side serving as the outlet of the film-forming resin solution in the porous element, and is referred to as the filtration area Refers to all the surfaces of the porous element that combine the opening and the non-opening of the secondary side to be the outlet of the film-forming resin solution. The filtration precision refers to the size of a removable object in the porous filter.

When composite layers are formed using a plurality of film-forming resin solutions, if the layers are not mixed, it is necessary to confirm the number of calculated junctions in each layer. For example, in the case of a two-layer structure of an inner layer and an outer layer, it is necessary to set the number of calculated joins to be 50 or more in each of the inner layer and the outer layer, and cracks tend to occur if the number of calculated joins is lower.

When the calculated number of confluences is reduced, cracks tend to occur along the axial direction when a physical load is applied to the hollow fiber membrane, and more cracks are less likely to occur. The number of the calculated merging is preferably 50 to 3,000, more preferably 200 to 2,500, and still more preferably 500 to 2,000. When the above-mentioned calculated merging number is within the above range, cracks along the axial direction are less likely to occur when a physical load is applied to the hollow fiber membrane.

The spinning nozzle 21 according to the second embodiment of the present invention has a solution reservoir 217 for storing the solution in the form of a circular ring in cross section. The liquid storage portion 217 is divided into a first liquid storage chamber 217A at the upper end and a second liquid storage chamber 217B at the lower end. As shown in Figs. 10 to 12, the first liquid storage chamber 217A communicates with the inlet portion 216 at an upper portion on one side of the outer wall, and has eight (eight) liquid storage portions 217A installed along the outer wall of the liquid storage portion 217 And communicates with the second liquid storage chamber 217B by the supply path 217a. That is, the film-forming resin solution flowing in the vicinity of the outer wall of the film-forming resin solution supplied to the first liquid storage chamber 217A flows through the respective supply passages 217a to the outer wall of the second liquid storage chamber 217B As shown in FIG.

11, the first liquid storage chamber 217A has an annular ring-shaped annular portion 217b and eight outer peripheral portions 217c formed to be recessed outward from the annular portion 217b. The first liquid storage chamber 217A communicates with the inlet portion 216 at an upper portion on the outer wall side in one outer peripheral portion 217c. The center of the annular portion 217b of the first liquid storage chamber 217A and the center of the support passage 214 coincide with each other.

The supply path 217a is provided with eight such that the respective outer peripheral portions 217c of the first liquid storage chamber 217A and the second liquid storage chamber 217B communicate with each other. That is, two or more supply passages 217a are provided along the outer wall of the liquid reservoir 217. [ The spinning nozzle 21 is arranged so that the supply path 217a for supplying the film-forming resin solution from the first liquid storage chamber 217A at the upper end to the second liquid storage chamber 217B below it is connected to the liquid storage portion 217, And two or more of them are provided so as to follow the outer wall. In the present invention, being provided along the outer wall of the liquid reservoir means that it follows the outermost outer wall when the liquid storage chamber having the outer peripheral portion 217c is formed on the outer side of the annular portion 217b as in this example. That is, in this example, the supply passage 217a is provided so as to follow the outer wall of the outer peripheral portion 217c, which is the outermost outer wall of the first liquid storage chamber 217A in the liquid storage portion 217. [

In the first liquid storage chamber 217A, as shown in Fig. 11, the film-forming resin solution supplied from the inlet portion 216 is divided into two portions from the side of the inlet portion 216 and circulated in an arc shape, 216 and the joining portion 217d on the opposite side. The film forming resin solution flowing in the vicinity of the outer wall of the first liquid storage chamber 217A is supplied from the outer peripheral portion 217c to the second liquid storage chamber 217B described later via the supply path 217a, And merged again in the second liquid storage chamber 217B so that the liquid is stored in an annular circular shape.

In the spinning nozzle 21, the liquid storage portion 217 is divided into a first liquid storage chamber 217A and a second liquid storage chamber 217B and the first liquid storage chamber 217A And the second liquid storage chamber 217B are provided in the porous film layer formed by the film-forming resin solution, it is possible to suppress the formation of a starting point of the crack along the axial direction. The factors by which the above-mentioned effects are obtained in the spinning nozzle 21 are not necessarily clear, but are considered as follows.

The inventors of the present invention have found that when the spinning nozzle is irradiated by a conventional spinning nozzle such as the spinning nozzle 1101 shown in Figs. 6 to 8, a starting point of a crack along the axial direction is formed in the porous film layer (FIG. 8) in which the film-forming resin solution branched on both sides of the liquid storage portion 1116 opposite to the introduction portion 1115, that is, , It has been found that a starting point of a crack along the axial direction is formed in the porous film layer. The entanglement of the film-forming resins tends to be smaller in the confluence portion 1116a than in the portion other than the confluence portion 1116a or the film formation can be suppressed by flowing in the vicinity of the outer wall of the liquid storage portion 1116, There is a possibility that the resin solution is concentrated, which is considered to be a factor for forming a starting point of the crack along the axial direction in the porous film layer.

On the other hand, in the spinning nozzle 21, the film-forming resin solution flowing in the vicinity of the outer wall in the first liquid storage chamber 217A of the liquid storage portion 217 is supplied from the two or more supply paths 217a to the second liquid And is supplied to the storage chamber 217B and stored in both the first liquid storage chamber 217A and the second liquid storage chamber 217B. As described above, in the liquid storage portion 217, since the film-forming resin solution repeats branching and joining, entanglement of the film-forming resin in the film-forming resin solution to be formed is consequently small as a whole, . In addition, since the outer peripheral portion 217c and the supply path 217a are provided, the film-forming resin flowing in the vicinity of the outer wall of the first liquid storage chamber 217A is dispersed in the circumferential direction and concentrated in the joining portion 217d Is avoided. Therefore, it is considered that formation of a starting point of a crack along the axial direction in the porous film layer is suppressed.

The first liquid storage chamber 217A is provided with an outer peripheral portion 217c on the outer side of the annular portion 217b and communicates with the outer peripheral portion 217c and the second liquid storage portion 217B, It is preferable to provide the supply path 217a. By providing the outer peripheral portion 217c having a concave shape outward from the annular portion 217b as described above, the film-forming resin solution flowing in the vicinity of the outer wall enters the outer peripheral portion 217c, The resin solution collects in the outer peripheral portion 217c and is easily supplied to the second liquid storage portion 217B through the supply path 217a.

The cross-sectional shape of the outer peripheral portion 217c is preferably a convex shape whose outer wall is curved outwardly from the ring portion 217b and bent to form one angle, as in this example. In this example, the shape when the eight outer peripheral portions 217c are viewed from above is a molded polygon formed by rotating two squares by 45 degrees.

However, the cross-sectional shape of the outer peripheral portion 217c is not limited to the convex shape but may be a semicircular shape or the like.

It is preferable that the outer peripheral portion 217c is uniformly provided on the outer side of the ring portion 217b in the same shape when viewed from above as in this example.

It is preferable that the outer peripheral portion 217c is formed such that the bottom surface is gradually lowered from the side communicating with the inlet portion 216 toward the opposite side as shown in Fig. That is, the bottom surface of the outer peripheral portion 217c on the side in which the inlet portion 216 communicates is the highest, and the bottom surface of the outer peripheral portion 217c on the opposite side to the side in which the inlet portion 216 communicates is the lowest desirable. By forming steps in the height direction of the outer peripheral portion 217c as described above, the film-forming resin solution flowing in the vicinity of the outer wall surface along the respective heights is divided into the outer peripheral portions 217c, And the film forming resin solution flowing in the vicinity of the outer wall is not collected in the joining portion 217d.

12 is a perspective sectional view showing only one side of the second nozzle 212. The other side of the second nozzle 212 likewise has an outer peripheral portion 217c so as to be gradually lowered from the side in which the inlet portion 216 is communicated, Respectively.

It is also preferable that a slit portion 217e is formed in the vicinity of the tab 218 in the first liquid storage chamber 217A as shown in Fig. Particularly, in the case where the uniformity of discharge in the circumferential direction is difficult to attain a desired level only by the film-forming resin solution flowing through the tubular portion 218, the application of the flow resistance in the slit portion 217e is carried out in the circumferential direction From the viewpoint of improving the uniformity of discharge in the discharge space.

The second liquid storage chamber 217B is a portion for storing a solution of the film-forming resin solution flowing from the first liquid storage chamber 217A through the supply path 217a into an endless circular shape.

10 and 13, similarly to the first liquid storage chamber 217A, the second liquid storage chamber 217B includes an annular ring-shaped annular ring portion 217f and an annular recessed portion 217f outwardly recessed from the annular portion 217f And eight outer peripheral portions 217g formed so as to be spaced apart from each other. The outer peripheral portion 217g of the second liquid storage portion 217B is formed on the upper side of the annular portion 217f such that the bottom surface thereof has a constant height. In the second liquid storage chamber 217B, the film-forming resin solution is supplied from the outer peripheral portion 217c of the first liquid storage chamber 217A to the outer peripheral portion 217g through the supply path 217a have.

The center of the ring portion 217f of the second liquid storage portion 217B and the center of the support passage 214 coincide with each other.

13, the film-forming resin solution supplied from the supply path 217a to each of the outer circumferential portions 217g is transferred from the outer wall to the central portion through the annular portion 217f, Respectively.

Sectional shape of the outer peripheral portion 217g of the second liquid storage portion 217B is preferably the same as the outer peripheral portion 217c of the first liquid storage portion 217A. In this example, the shape when the eight outer peripheral portions 217g are viewed from above is a molded polygon formed by aligning two squares by 45 degrees.

It is preferable that the outer peripheral portion 217g is uniformly provided on the outer side of the ring portion 217f in the same shape when viewed from above, as in this example.

It is preferable that a slit portion 217h is formed in the vicinity of the negative portion 218 in the second liquid storage portion 217B as shown in Fig. Particularly, in the case where the uniformity of discharge in the circumferential direction is difficult to attain a desired level by merely allowing the film-forming resin solution to flow through the tubular portion 218, the application of the flow resistance in the slit portion 217h is preferably performed in the circumferential direction From the viewpoint of improving the uniformity of the discharge in the discharge space.

The film-forming resin solution stored in the second liquid storage part 217B passes through the slit part 217h and joins with the film-forming resin solution from the first liquid storage chamber 217A at the negative part 218. [

The supply path 217a is a portion for supplying the film-forming resin solution flowing in the vicinity of the outer wall of the first liquid storage chamber 217A to the second liquid storage chamber 217B.

The cross-sectional shape of the supply path 217a is preferably circular as in this example. However, the cross-sectional shape of the supply path 217a is not limited to a circular shape.

The diameter of the supply path 217a is not particularly limited.

The number of supply paths 217a is eight in this example, but may be seven or less, or nine or more. The number of the supply paths 217a may be set appropriately in consideration of the diameter and length of the supply path 217a to be formed, the area of the bottom surface where the supply path 217a can be formed in the first liquid storage chamber 217A, and the like .

It is preferable that the two or more supply paths 217a are uniformly provided along the outer wall of the liquid storage portion 217 since the film forming resin can be uniformly supplied to the second liquid storage chamber 217B at the lower end.

The shaping resin solution injected from the first liquid storage chamber 217A and the second liquid storage chamber 217B of the liquid storage portion 217 is passed through the supporter passage 214 and concentrically And is a portion which is formed by circulating in the form of a circular cylinder.

The width (distance between the inner wall and the outer wall) of the hollow portion 218 can be appropriately set in accordance with the thickness of the porous film layer to be formed.

In the spinning of the porous hollow fiber membrane by the spinning nozzle 21, the hollow support is fed from the support feed port 214a to the support passage 214, and the film forming resin solution is fed in a constant amount, The resin solution is supplied to the resin flow path 215 from the resin supply port 215a.

In the resin flow path 215, the film-forming resin solution flowing through the inlet portion 216 flows into the first liquid storage chamber 217A of the liquid storage portion 217, and in the first liquid storage chamber 217A, Flows into the arcuate shape and then joins in the joining portion 217d and flows into the hollow portion 218 through the slit portion 217e. At this time, the film-forming resin solution flowing in the vicinity of the outer wall of the first liquid storage chamber 217A enters each outer peripheral portion 217c and is supplied to the second liquid storage chamber 217B through the supply passage 217a. The film-forming resin solutions supplied to the respective outer peripheral portions 217g of the second liquid storage chamber 217B through the supply path 217a flow into the annular portion 217f while joining them from the outer wall toward the central portion, (217h). ≪ / RTI > The film-forming resin solution formed in the cylindrical shape in the tubular portion 218 is applied to the outside of the support discharged from the discharge port 215b and simultaneously drawn out from the support outlet 214b.

Thereafter, for example, in a container for bringing a film containing a water-containing gas into contact with the film-forming resin solution, the film-forming resin solution is allowed to pass through a coagulation bath in which the film-forming resin solution is brought into contact with the coagulating solution, , Or drying or the like to obtain a hollow fiber membrane.

The liquid storage portion 316 according to the third embodiment of the present invention is a portion for storing liquid by making the film-forming resin solution flowing through the introduction portion 315 into an annular circular shape. The introduction portion 315 communicates with one of the outer wall sides of the liquid storage portion 316.

The cross-sectional shape of the liquid storage portion 316 is a circular shape as shown in Fig. The liquid storage portion 316 of this example has a cylindrical portion 316a having a constant diameter and a sharply inclined portion 316b so that the diameter of the lower portion of the cylindrical portion 316a gradually decreases. The liquid storage portion 316 is not limited to the tubular portion 316a and the inclined portion 316b as long as it can store the film-forming resin solution flowing through the introduction portion 315, A hollow portion used for a hollow fiber spinning nozzle can be employed. The liquid storage portion 316 is preferably circular in cross section as in this example. However, the cross-sectional shape of the liquid storage portion 118 is not limited to the circular cross-section.

The center of the liquid storage portion 316 and the center of the support passage 313 coincide with each other.

17 and 18, the spinning nozzle 31 is provided with a filling layer 320 filled with the branching and merging means, that is, the particle 321, in the liquid storing portion 316 . By providing the filling layer 320, it is possible to suppress the formation of a starting point of a crack along the axial direction in the porous film layer formed by the film-forming resin solution. In the spinning nozzle 31, the factor by which the above effect is obtained by the filling layer 320 is not necessarily clear, but is considered as follows.

The inventors of the present invention have found that when the spinning nozzle is irradiated by a conventional spinning nozzle such as the spinning nozzle 1101 shown in Figs. 6 to 8, a starting point of a crack along the axial direction is formed in the porous film layer (FIG. 8) in which the film-forming resin solution branched on both sides of the liquid storage portion 1116 opposite to the introduction portion 1115, that is, , It has been found that a starting point of a crack along the axial direction is formed in the porous film layer. In this confluence portion 1116a, entanglement of the film-forming resins tends to be smaller than portions other than the confluence portion 1116a, which is a stress concentration point when a load such as flatness is generated, It is considered that the starting point is formed.

On the other hand, in the spinning nozzle 31, the film-forming resin solution passing through the gap of the particles 321 in the filling layer 320 in the liquid storage portion 316 is subjected to three- The entanglement of the film-forming resin in the film-forming resin solution is consequently reduced as a whole. As a result, the film-forming resin solution is homogenized in the spinning nozzle of the present invention, It is considered that formation of a starting point of the crack along the axial direction is suppressed.

The shape of the particles 321 is spherical in this example. However, the shape of the particles 321 is not limited to a spherical shape, but may be a rectangular shape, a pillar shape, or a non-uniform three-dimensional structure.

The material of the particles 321 is not particularly limited and may be selected from metals such as stainless steel and alloys, inorganic materials such as glass and ceramics, resins which are not immersed in a film-forming resin solution such as Teflon (registered trademark) .

Specific examples of the particles 321 include steel balls and the like.

The size of the particle 321 may be such that it can be filled in the liquid reservoir 316 and can maintain the shape of the filling layer 320 without flowing into the hollow portion 317. The smaller the size of the particle 321 is, the smaller the size of the film formed by the gap of the particles 321 in the filling layer 320 becomes, as long as the size of the particle 321 is within the range in which the filling layer 320 can be held in the liquid storage portion 316 The flow path through which the resin resin solution flows is more finely branched and merged three-dimensionally, so that the uniformity of the film-forming resin solution inside the spinning nozzle of the present invention tends to be facilitated.

The number of the particles 321 may be a number sufficient to form the filling layer 320 by filling the particles 321 in the liquid storage portion 316 and the size of the particles 321, 316, the height of the filling layer 320 to be formed, and the like.

The liquid reservoir 316 may be filled with particles 321 having the same shape, material, and size, or may be filled with particles 321 having different shapes, materials, and sizes. Further, two or more different filling layers may be laminated in the direction in which the film-forming resin solution flows to form a gradient of the gap.

17, the distance between the lower end of the lowest particle 321 in the filling layer 320 and the upper end of the uppermost particle 321 in the filling layer 320 is And the height h of the filling layer 320. The upper limit of the height h of the filling layer 320 is equal to or less than the height of the liquid storage portion 316, that is, the height of filling the particles 321 in the liquid storage portion 316 as a whole. When the height h of the filling layer 320 is increased, the flow paths through which the film-forming resin solution flows are more finely branched and merged three-dimensionally. Thus, the film- There is a tendency that the uniformity of the magnetic field becomes easy. On the other hand, if the height h of the filling layer 320 is excessively high, the differential pressure increases rapidly due to the excess of the apparatus or the increase of the initial pressure when the film-forming resin solution flows through the filling layer 320, There is a possibility that the long-term stable emission may become difficult, for example, the life is shortened.

The height h of the packed layer 320 is preferably set so that the viscosity and the characteristics of the film-forming resin solution or the size of the charged particles Or the like, depending on the desired conditions.

A space portion is formed above the filling layer 320 of the liquid storage portion 316 before the film-forming resin solution supplied to the liquid storage portion 316 is supplied to the space portion And then supplied to the filling layer 320 after passing. Thus, the passing state of the filling layer 320 in the circumferential direction inside the spinning nozzle of the film-forming resin solution of the present invention is made uniform.

The tubular portion 317 is a portion circulating in the shape of an annular ring in the liquid storage portion 316 to circulate the film-forming resin solution stored in the liquid in the form of a concentric circular cylinder with a supporter through which the supporter passage 313 passes. The liquid storage portion 317 is preferably circular in cross section as in this example. However, the cross-sectional shape of the liquid storage portion 317 is not limited to the circular cross-section.

The width (distance between the inner wall and the outer wall) of the hollow portion 317 can be appropriately set in accordance with the thickness of the porous film layer to be formed.

In the spinning of the porous hollow fiber membrane by the spinning nozzle 31, the hollow support is fed from the support feed port 313a to the support passage 313, and the film-forming resin solution is fed in a constant amount, The resin solution is supplied to the resin flow path 314 from the resin supply port 314a.

In the resin flow path 314, the film-forming resin solution flowing through the inlet portion 315 flows into the liquid storage portion 316, flows in an arc shape on both sides and merges on the opposite side of the inlet portion 315, The gap between the first and second electrodes 321 passes through the filling layer 320 and flows into the hollow portion 317 while repeating minute branching and merging.

The film-forming resin solution formed into a cylindrical shape by the hollow portion 317 is applied to the outside of the support discharged from the discharge port 314b and derived from the support outlet 313b.

Thereafter, for example, in a container for bringing a film containing a water-containing gas into contact with the film-forming resin solution, the film-forming resin solution is allowed to pass through a coagulation bath in which the film-forming resin solution is brought into contact with the coagulating solution, , Or drying or the like to obtain a hollow fiber membrane.

The liquid storage portion 416 according to the fourth embodiment of the present invention includes a first liquid storage portion 416A, a second liquid storage portion 416B, a third liquid storage portion 416C, a fourth liquid storage portion 416D). The first liquid storage portion 416A is a portion for storing liquid by making the film-forming resin solution circulating in the introduction portion 415 into an annular shape and the second liquid storage portion 416B is a portion for storing the first resin supply portion 416a , The third liquid reservoir 416C serves as the second resin supply portion 416b and the fourth liquid reservoir 416D serves as a ring-shaped film-forming resin solution circulating the third resin supply portion 416c It is the part to store the liquid. As shown in Figs. 23 and 24, the first liquid storage portion 416A and the second liquid storage portion 416B communicate with the first resin supply portion 416a, and as shown in Figs. 25 and 26 27 and 28, the second liquid reservoir 416B and the third liquid reservoir 416C communicate with each other at the second resin supply portion 416b, and the third liquid reservoir 416C and the third liquid reservoir 416C communicate with each other. And the fourth liquid storage portion 416D communicate with the third resin supply portion 416c.

The cross sectional shapes of the first liquid storage portion 416A, the second liquid storage portion 416B, the third liquid storage portion 416C and the fourth liquid storage portion 416D are the same as those of Figs. 23, 25, 29, and the central axes of the first liquid storage portion 416A to the fourth liquid storage portion 416D coincide with the central axes of the support passage 413. However, the cross-sectional shapes of the cross-sectional shapes of the first liquid storage portion 416A, the second liquid storage portion 416B, the third liquid storage portion 416C, and the fourth liquid storage portion 416D are limited It does not.

In each of the first liquid storage portion 416A, the second liquid storage portion 416B, the third liquid storage portion 416C and the fourth liquid storage portion 416D in the liquid storage portion 416, The resin solution is divided into two parts and circulated in an arc shape. Specifically, in the first liquid storage portion 416A, as shown in Figs. 22 and 23, the film-forming resin solution flowing through the inlet portion 415 flows in an arc shape and branches to both sides and joins . 24 and 25, the film-forming resin solution flowing through the first resin supply portion 416a from the first liquid storage portion 416A is supplied to the second liquid storage portion 416B via the branch And circulates and joins in an arc shape. 26 and 27, the film-forming resin solution flowing from the second liquid storage portion 416B through the second resin supply portion 416b is discharged to both sides Branched and circulated in an arc shape and joined together. 28 and 29, the film-forming resin that has flowed from the third liquid storage portion 416C through the third resin supply portion 416c flows in the fourth liquid storage portion 416D, Flows in an arc shape, and joins at the opposite side of the third resin supply portion 416c.

22, the upper sides of the first liquid storage part 416A, the second liquid storage part 416B, the third liquid storage part 416C, and the fourth liquid storage part 416D are located at the center The film-forming resin solution communicates with the first, second, and third cylindrical portions 417A, 417B, 417C, and 417D, respectively, which are cylindrically shaped. That is, from each of the first liquid storage part 416A, the second liquid storage part 416B, the third liquid storage part 416C and the fourth liquid storage part 416D, The solution is allowed to flow into the first, second and third tubular portions 417A, 417B, 417C and 417D.

In the spinning nozzle 41, as described above, the liquid storage portion is divided into two or more stages so as to circulate the film-forming resin solution in the form of an arc, so that the porous film layer formed by the film- It is suppressed that a starting point of the crack due to the crack is formed. The factors by which the above-mentioned effects are obtained in the spinning nozzle 41 are not necessarily clear, but are considered as follows.

The inventors of the present invention have found that, in the spinning by the conventional spinning nozzle such as the spinning nozzle 1101 exemplified in Figs. 6 to 8, when the spinning speed is increased, the starting point of the crack along the axial direction is formed in the porous film layer A portion corresponding to the joining portion 1116a (FIG. 8) where the film-forming resin solution branched on both sides of the liquid storage portion 1116 joins again, , It has been found that a starting point of a crack along the axial direction is formed in the porous film layer. In this confluence portion 1116a, entanglement of the film-forming resins tends to be smaller than portions other than the confluence portion 1116a, which is a stress concentration point when a load such as flatness is generated, It is considered that the starting point is formed.

On the other hand, in the liquid storage part 416 of the spinning nozzle 41, the first liquid storage part 416A, the second liquid storage part 416B, the third liquid storage part 416C and the fourth liquid storage part 416D ), The branching and merging of the film-forming resin solution is carried out two or more times. As a result, entanglement of the film-forming resin in the film-forming resin solution to be formed becomes consequently small as a whole, and the film-forming resin solution is homogenized in the spinning nozzle of the present invention. In addition, since the confluent portions of the film-forming resin solutions in the respective liquid storage portions are at different positions, it is avoided that the confluent portions are formed to be connected in the thickness direction of the film. Therefore, it is considered that formation of a starting point of the crack along the axial direction is suppressed.

The hollow fiber spinning nozzle according to the fourth aspect of the present invention is characterized in that the liquid storage portion is divided into three or more stages as in the spinning nozzle 41 of this example and the liquid storage portion in the n-th stage (n is a natural number) It is preferable that the resin supply section which communicates the liquid storage section and the resin supply section which communicates the liquid storage section of the (n + 1) th stage and the liquid storage section of the (n + 2) th stage is disposed at a position shifted in the circumferential direction of the liquid storage section. Specifically, as shown in Figs. 23 and 25, the first liquid storage portion 416A of the first stage and the second liquid storage portion 416B of the second stage, The second resin supply portion 416b for communicating the second liquid storage portion 416B of the second stage and the third liquid storage portion 416C of the third stage communicates with the liquid storage And is arranged to be shifted in the circumferential direction of the portion 416. Likewise, as shown in Figs. 25 and 27, a second resin supply portion 416b for communicating the second liquid storage portion 416B of the second stage and the third liquid storage portion 416C of the third stage, A third resin supply portion 416c for communicating the third stage liquid storage portion 416C of the third stage and the fourth liquid storage portion 416D of the fourth stage is arranged to be shifted in the circumferential direction of the liquid storage portion 416 . As a result, it is possible to avoid that the joining portions of the film-forming resin solutions in the respective liquid storage portions are gathered at the same position in the circumferential direction of the liquid storage portion, so that the hollow fiber membranes, Can be easily obtained.

The hollow fiber spinning nozzle according to the fourth aspect of the present invention is characterized in that each resin supply section is arranged at a predetermined angular interval in the circumferential direction of the liquid storage section with respect to the central axis of the annular section, It is more preferable to arrange them. In the spinning nozzle 41, the first resin supply portion 416a, the second resin supply portion 416b and the third resin supply portion 416c are shifted by 225 ° in the counterclockwise direction along the circumferential direction of the liquid storage portion 416 Are arranged at equal angular intervals. This makes it easier to obtain a hollow fiber membrane in which cracking along the axial direction is less likely to occur.

In the first liquid storage portion 416A, a slit portion 416d may be formed in the vicinity of the first cylindrical portion 417A as shown in Fig. By providing the flow resistance by forming the slit portion 416d, the uniformity of the discharge in the circumferential direction of the film-forming resin solution can be improved.

Likewise, the second liquid reservoir 416B, the third liquid reservoir 416C and the fourth liquid reservoir 416D are also connected to the second, third and fourth subsections 417B, 417C, 417C, The slit portions 416e, 416f, and 416g may be formed in the vicinity of each of the slits 417E, 417D, 417D.

The first resin supply portion 416a is a portion for supplying the film-forming resin solution flowing through the first liquid storage portion 416A to the second liquid storage portion 416B. The second resin supplying portion 416b is a portion for supplying the film forming resin solution flowing through the second liquid storing portion 416B to the third liquid storing portion 416C and the third resin supplying portion 416c And supplies the film-forming resin solution flowing through the third liquid storage portion 416C to the fourth liquid storage portion 416D.

The cross-sectional shape of the first resin supply portion 416a is preferably circular as in this example. However, the sectional shape of the first resin supply portion 416a is not limited to a circular shape. The diameter of the first resin supply portion 416a is not particularly limited.

Sectional shapes and diameters of the second resin supply portion 416b and the third resin supply portion 416c are the same as those of the first resin supply portion 416a and the preferred embodiments are also the same.

The first shaping section 417A is a portion formed into a cylindrical shape concentric with the support for allowing the film-forming resin solution flowing from the first liquid storage section 416A to pass through the support passage 413.

The second mold section 417B is formed by laminating a film-forming resin solution flowing from the second liquid storage section 416B outside the film-forming resin that has flown through the first mold section 417A, 413) and a cylindrical portion formed concentrically with the support.

The third mold section 417C is formed by laminating a film-forming resin solution flowing from the third liquid storage section 416C to the outside of the film-forming resin that has flown through the second mold section 417B, 413) and a cylindrical portion formed concentrically with the support.

The fourth mold section 417D is formed by laminating a film-forming resin solution flowing from the fourth liquid storage section 416D outside the film-forming resin that has flown through the third mold section 417C, 413) and a cylindrical portion formed concentrically with the support.

The widths (the distance between the inner wall and the outer wall) of the first, second and third tubular portions 417A, 417B, 417C, 417C, .

The lengths of the first, second, third and fourth bulb portions 417A, 417B, 417C and 417D are not particularly limited.

In the spinning of the porous hollow fiber membrane by the spinning nozzle 41, a hollow support is fed from the support feed port 413a to the support channel 413, and a device for feeding a film-forming resin solution in a fixed amount (for example, The film forming resin solution is supplied from the resin supply port 414a to the resin flow path 414 by a positive displacement pump such as a gear pump.

In the resin flow path 414, as shown in Figs. 22 and 23, the film-forming resin solution flowing through the inlet portion 415 flows into the first liquid storage portion 416A, and the first liquid storage portion 416A , And flows into the first bulb portion 417A through the slit portion 416d while flowing and merging into the arc shape.

23 and 24, the film-forming resin solution joined in the first liquid storage portion 416A is supplied to the second liquid storage portion 416B through the first resin supply portion 416a ≪ / RTI >

In the second liquid storage portion 416B, as shown in Fig. 22 and Fig. 25, the film-forming resin solution is branched on both sides and circulates and joins in an arc shape, (417B) and is laminated so as to cover the outer periphery of the film-forming resin solution flowing through the first negative section (417A). 25 and 26, the film-forming resin solution joined in the second liquid storage portion 416B is supplied to the third liquid storage portion 416C through the second resin supply portion 416b ≪ / RTI >

Similarly, as shown in Figs. 22 and 27, the film-forming resin solution is branched into two and circulated and joined together in an arc shape in the third liquid storage part 416C, Is introduced into the tubular portion 417C and laminated so as to cover the outer periphery of the film-forming resin solution which has been stacked and flowed in the second tubular portion 417B. 27 and 28, the film-forming resin solution joined in the third liquid storage portion 416C flows into the fourth liquid storage portion 416D through the third resin supply portion 416c do.

As shown in Figs. 22 and 29, the film-forming resin solution also divides in the fourth liquid storage part 416D and circulates and merges in an arc shape, and flows through the slit part 416g, And is laminated so as to cover the outer periphery of the film-forming resin solution that has flown into the third section 417C.

As described above, in the second negative section 417B, the film-forming resin solution flows in from the first negative section 417A and the second liquid storage section 416B, and is merged and laminated. In the third negative section 417C, The film forming resin solution flows in from the second and third liquid reservoirs 417B and 416C to be merged and laminated. In the fourth liquid portion 417D, the third liquid portion 417C and the fourth liquid And the film-forming resin solution flows in from the storage portion 416D to be joined and laminated. In this manner, the film-forming resin solution in the form of a cylinder in the form of a cylinder in the fourth tubular portion 417D is applied to the outside of the support discharged from the discharge port 414b and derived from the support outlet 413b.

Thereafter, for example, in a container for bringing a film containing a water-containing gas into contact with the film-forming resin solution, the film-forming resin solution is allowed to pass through a coagulation bath in which the film-forming resin solution is brought into contact with the coagulating solution, , Or drying or the like to obtain a hollow fiber membrane.

The liquid storage portion 516 is a portion for forming the film-forming resin solution flowing through the introduction portion 515 in an annular circular shape. The introduction portion 515 communicates with one of the outer wall sides of the liquid storage portion 516.

The cross-sectional shape of the liquid storage portion 516 is an annular shape as shown in Fig. 32, and the center of the liquid storage portion 516 and the center of the support passage 513 coincide with each other. In the liquid storage portion 516, the film-forming resin solution flows into the arc shape branched on both sides from the side of the introduction portion 515 and merges at the joining portion 516a on the opposite side of the introduction portion 515. The liquid storage portion 516 is preferably circular in cross section as in this example. However, the cross-sectional shape of the liquid storage portion 516 is not limited to the circular cross section.

31, it is preferable that a slit portion 516b is formed in the liquid storage portion 516 in the vicinity of the meandering portion 518. As shown in Fig. By providing the flow resistance by forming the slit portion 516b, the uniformity of the discharge in the circumferential direction of the film-forming resin solution can be improved.

The spinning nozzle 51 is characterized in that it has a meandering portion 518 between the liquid storage portion 516 and the tubular portion 517 as shown in Figs. 31, 33, and 34. Fig. The meandering portion 518 has two first dams 511a in an annular ring shape extending from the first nozzle 511 toward the second nozzle 512 and a second dam 511b extending from the second nozzle 512 to the first nozzle 511. [ And two second dams 512a each having an annular circular cross section extending toward the second dams 512a. The first dam 511a and the second dam 512a are arranged alternately.

The meandering portion 518 is formed by the first dike 511a and the second dike 512a in the shape of a concentric circle with five annular oil passage portions 518a to 518e having an annular circular ring shape and different diameters, The annular passage portion 518a communicates with the annular passage portion 518b from the outer wall side and the annular passage portion 518b and the annular passage portion 518c communicate with each other from the upper side, The flow path portion 518d communicates with the lower side, and the annular flow path portion 518d and the annular flow path portion 518e communicate with each other from above. The inner wall side of the liquid storage portion 516 communicates with the annular flow passage portion 518a of the serpentine portion 518 and the annular flow passage portion 518e of the serpentine portion 518 communicates with the annular portion 517 .

As described above, the meandering portion 518 is configured so that the film-forming resin flowing in from the liquid storage portion 516 flows in a meandering shape upward and downward toward the center in a state in which the sectional shape thereof is maintained in a circular shape.

By providing the meandering portion 518 in the spinning nozzle 51, it is possible to suppress the formation of a starting point of the crack along the axial direction in the porous film layer formed by the film-forming resin solution. In the spinning nozzle 51, the factor by which the above-described effect is obtained by the above-described meandering portion 518 is not necessarily clear, but is considered as follows.

The inventors of the present invention have found that when the spinning nozzle is irradiated by a conventional spinning nozzle such as the spinning nozzle 1101 shown in Figs. 6 to 8, a starting point of a crack along the axial direction is formed in the porous film layer (FIG. 8) in which the film-forming resin solution branched on both sides of the liquid storage portion 1116 opposite to the introduction portion 1115, that is, , It has been found that a starting point of a crack along the axial direction is formed in the porous film layer. In this joining portion 1116a, the entanglement of the film-forming resins tends to be smaller than the portion other than the joining portion 1116a, and this is a stress concentration point at the time of generation of a load such as a flattening, It is believed that this is a factor that forms the film.

On the other hand, in the spinning nozzle 51, the meandering portion 518 is provided so that the path from the liquid storage portion 516 to the discharge port 514b is the path of the negative portion 1116 ) To the discharge port 1114b, and the time for which the film-forming resin solution stays in the nozzle is prolonged. Therefore, even if entanglement of the film-forming resin of the film-forming resin solution in the confluent portion 516a (FIG. 32) of the liquid storage portion 516 is smaller than entanglement of the portion other than the confluent portion 516a , It is believed that the entanglement returns to the state before the branching during circulation in the meandering portion 518 and the uniformity of the entire inside of the spinning nozzle of the present invention is suppressed from forming the origin of the crack along the axial direction in the formed porous film layer .

The width (lateral length) of the flow path from the annular flow path portion 518a to the annular flow path portion 518e in the meandering portion 518 and the height of the dike 511a and the dike 512a, It is preferable to set the average flow rate of the film-forming resin solution to be maximized.

The embossed portion 517 is a portion formed in a concentric circular cylindrical shape with a supporter through which the film-forming resin solution flowing through the meandering portion 518 passes through the supporter passage 513. [

The width (distance between the inner wall and the outer wall) of the hollow portion 517 can be appropriately set in accordance with the thickness of the porous film layer to be formed and the desired adhering condition.

In the spinning of the porous hollow fiber membrane by the spinning nozzle 51, a hollow support is fed from the support feed port 513a to the support channel 513 and a device for feeding a film-forming resin solution in a fixed amount (for example, The film forming resin solution is supplied from the resin supply port 514a to the resin flow path 514 by a positive displacement pump such as a gear pump.

In the resin flow path 514, the film-forming resin solution flowing through the introduction portion 515 flows into the liquid storage portion 516, flows in an arc shape on both sides and then joins on the opposite side of the introduction portion 515, And flows into the meandering portion 518. Then, in the meandering portion 518, the film-forming resin solution flows upward and downward in a meandering state while keeping the sectional shape thereof in an annular shape, flows toward the center direction, and flows into the hollow portion 517. The film-forming resin solution formed into a cylindrical shape in the tubular portion 517 is applied to the outside of the support discharged from the discharge port 514b and derived from the support outlet 513b.

Thereafter, for example, in a container for bringing a film containing a water-containing gas into contact with the film-forming resin solution, the film-forming resin solution is allowed to pass through a coagulation bath in which the film-forming resin solution is brought into contact with the coagulating solution, , Or drying or the like to obtain a hollow fiber membrane.

The liquid storage portion 616 is a portion for storing the liquid of the film-forming resin solution flowing through the inlet portion 615 in an annular circular shape. The liquid storage portion 616 is preferably circular in cross section as in this example. However, the cross-sectional shape of the liquid storage portion 616 is not limited to the circular cross-section.

37 to 39, in the liquid storage portion 616 of the spinning nozzle 61, the liquid storage portion 616 extends from the lower wall surface 616a toward the upper wall surface 616b, 618 are provided. The dam 618 and the dam 619 are formed continuously from the outer wall side of the liquid reservoir 616 toward the inner wall side and are connected to each other in the vicinity of the inner wall of the liquid reservoir 616. Thereby, vortex flow passages 616c and 616d are formed in the liquid storage portion 616, through which the film-forming resin solution circulates while swirling. The vortex flow passage 616c communicates with the inlet portion 615 and is a different path from the vicinity of the inner wall of the liquid storage portion 616 and the vortex flow passage 616d has a different path from the outer wall side of the liquid storage portion 616 And communicates with the tubular portion 617 on the inner wall side. The flow of the film-forming resin solution in the liquid storage portion 616 is regulated so as to swirl in a spiral shape by the dams 618 and 619.

37, there is a clearance between the upper portion of the dam 618 and the dam 619 and the upper wall surface 616b of the liquid storage portion 616, as shown in Fig. Thereby, the film-forming resin solution supplied into the liquid storage portion 616 is allowed to ride over the dam 618 and the dam 619 while turning in a spiral shape toward the center direction.

The number of revolutions of the spiral-shaped dam is preferably 2 or more and 10 or less, more preferably 3 or more, or 7 or less, and more preferably 4 or more or 5 or less. If the number of revolutions is two or more, the film-forming resin solution is uniform in the spinning nozzle of the present invention.

In the spinning nozzle 61, the liquid reservoir 616 is provided with dams 618 and 619 for regulating the circulation of the film-forming resin solution in the liquid reservoir 616 in a spiral shape as described above, It is possible to suppress generation of a starting point of a crack along the axial direction in the porous film layer formed by the film-forming resin solution. The reason why the above effect can be obtained in the liquid storage portion 616 of the spinning nozzle 61 is not clear, but is considered as follows.

The inventors of the present invention have found that when the spinning nozzle is irradiated by a conventional spinning nozzle such as the spinning nozzle 1101 shown in Figs. 6 to 8, a starting point of a crack along the axial direction is formed in the porous film layer (FIG. 8) in which the film-forming resin solution branched on both sides of the liquid storage portion 1116 on the opposite side to the introduction portion 1115, that is, It has been found that the starting point of the crack is formed along the axial direction in the porous film layer. In this joining portion 1116a, the entanglement of the film-forming resins tends to be smaller than the portion other than the joining portion 1116a. This tends to be a stress concentration point when a load such as flatness is generated, It is considered that the starting point is formed.

On the other hand, in the spinning nozzle 61, the film-forming resin solution in the liquid storage portion 616 circulates while overhanging the banks 618 and 619 while swirling in a spiral shape, and fine branching and joining are repeated, It is considered that the confluent boundary of the film-forming resin solution is prevented from being formed along a straight line passing through the central axis of the liquid reservoir 616 between the inner wall surface of the reservoir 616 and the outer wall surface. As a result, the entanglement and the confluence boundary of the film-forming resin in the film-forming resin solution stored in the liquid storage portion 616 are consequently reduced as a whole, and the film-forming resin solution It is considered that formation of a starting point of a crack along the axial direction in the formed porous film layer is suppressed.

The length of the gap between the vortex channels 616c and 616d and the gap between the weirs 618 and 619 and the upper wall surface 616b of the liquid reservoir 616 is not particularly limited as long as the above- .

37, a slit portion 616e may be formed in the liquid storage portion 616 in the vicinity of the bulb portion 617. In this case, By providing the flow resistance by forming the slit portion 616e, the uniformity in the circumferential direction in the discharge of the film-forming resin solution is improved.

The tubular portion 617 is a portion formed in the liquid storage portion 616 to form a film-forming resin solution stored in the form of an annular ring in a concentric cylindrical form with the support.

The width of the negative portion 617 (distance between the inner wall and the outer wall) can be appropriately set in accordance with the thickness of the porous film layer to be formed.

In the spinning of the hollow fiber membrane by the spinning nozzle 61, a hollow support is fed from the support feed port 613a to the support channel 613, and a device (for example, a gear The film forming resin solution is supplied from the resin supply port 614a to the resin flow path 614 by a positive displacement pump such as a pump.

In the resin flow path 614, the film-forming resin solution that has flowed through the inlet portion 615 is supplied to the liquid storage portion 616, and the dams 618 and 619 are supplied to the liquid storage portion 616 while swirling in the liquid storage portion 616 And flows into the hollow portion 617 while being circulated and circulated in an annular circular shape while repeating branching and joining. The film-forming resin solution formed into a cylindrical shape by the negative electrode portion 617 is discharged from the discharge port 614b and is applied to the outside of the support member led out from the support outlet 613b.

Thereafter, for example, in a container for bringing a film containing a water-containing gas into contact with the film-forming resin solution, the film-forming resin solution is allowed to pass through a coagulation bath in which the film-forming resin solution is brought into contact with the coagulating solution, , Or drying or the like to obtain a hollow fiber membrane.

[Second Embodiment]

Hereinafter, another embodiment of the hollow fiber spinning nozzle according to the sixth aspect of the present invention will be described. 41 to 43 are schematic views showing a hollow fiber spinning nozzle 62 (hereinafter referred to as " spinning nozzle 62 ") which is another embodiment of the hollow fiber spinning nozzle according to the sixth embodiment of the present invention.

The spinning nozzle 62 is a spinning nozzle for producing a hollow fiber membrane having a porous film layer formed on the outer side of a hollow support.

The spinning nozzle 62 of the present embodiment has a first nozzle 621 and a second nozzle 622 as shown in Figs.

As shown in Fig. 42, the spinning nozzle 62 has a support passage 623 for passing a hollow support and a resin flow passage 624 for flowing a film-forming resin solution for forming a porous film layer. 41 to 43, the resin flow path 624 has an inlet portion 625 into which the film-forming resin solution is introduced, and a liquid storage portion 625 in which the film- And a negative portion 627 which forms a film-forming resin solution stored in an annular circular ring shape in the liquid storage portion 626 in a concentric cylindrical form with the support passage 623.

The spinning nozzle 62 is configured such that the hollow support is supplied from the support supply port 623a and is led out from the support outlet 623b and the film forming resin solution is supplied from the resin supply port 624a to the resin flow path 624 And stored in the liquid storage portion 626. The liquid is stored in a concentric cylindrical shape in the negative portion 627 and discharged from the discharge port 624b in a cylindrical shape around the support.

As the material of the first nozzle 621 and the second nozzle 622, those commonly used as the spinning nozzle of the hollow fiber membrane can be used, and stainless steel (SUS) is preferable from the viewpoints of heat resistance, corrosion resistance, strength and the like.

The support passage 623 has a circular cross-sectional shape.

The diameter of the support passage 623 may be set appropriately in accordance with the diameter of the hollow support member to be used.

The cross-sectional shape of the inlet portion 625 of the resin flow path 624 is preferably circular as in this example. However, the cross-sectional shape of the introduction portion 625 is not limited to a circular shape.

The diameter of the inlet portion 625 is not particularly limited.

The liquid storage portion 626 is a portion for storing a solution of the film-forming resin solution flowing through the introduction portion 625 in an annular circular shape.

41 to 43, the liquid storage portion 626 of the spinning nozzle 62 extends from the inner wall surface 626a of the liquid storage portion 626 toward the outer wall surface 626b The weirs 628 are continuously provided in a spiral shape. As a result, a spiral flow path 626c is formed in the liquid storage portion 626, through which the film-forming resin solution circulates in a spiral shape. The introduction portion 625 is communicated at the side of the outer wall surface 626b of the liquid storage portion 626 and the flow of the film forming resin solution in the liquid storage portion 626 is formed by the dam 628 in the form of a spiral .

As shown in Fig. 43, there is a gap between the front end on the outer wall surface 626b side of the dam 628 and the outer wall surface 626b. Thereby, the film-forming resin solution supplied into the liquid storage portion 626 is made to fall downward from the outer wall surface 626b side of the dam 628 while rotating in a spiral shape along the spiral flow path 626c .

In the spinning nozzle 62, a dam 628 for regulating the flow of the film-forming resin solution in the liquid storage portion 626 in a spiral shape is provided in the liquid storage portion 626 as described above , It is possible to suppress the generation of a starting point of cracks along the axial direction in the porous film layer formed by the film-forming resin solution. The reason why the above effect can be obtained in the liquid storage portion 626 of the spinning nozzle 62 is not clear, but is considered to be similar to the spinning nozzle 61 described above.

That is, in the spinning nozzle 62, the film-forming resin solution in the liquid storage portion 626 circulates in a spiral shape so as to fall downward from the outer wall surface 626b side of the dike 628, The confluent boundary between the inner wall surface 626a and the outer wall surface 626b of the liquid storage portion 626 is set so that the confluent boundary of the film-forming resin solution flows in the horizontal direction passing through the central axis of the liquid storage portion 626 It is considered that formation along the straight line is suppressed. As a result, the entanglement and the confluence boundary of the film-forming resin in the film-forming resin solution stored in the liquid reservoir 626 as a whole becomes consequently small as a whole. As a result, in the spinning nozzle of the present invention, And the stress at the time of generation of load such as flatness is dispersed, so that it is considered that formation of a starting point of a crack along the axial direction in the formed porous film layer is suppressed.

The height of the helical flow path 626c (the distance between the upper and lower portions of the spiral-shaped dam 628) is not particularly limited.

The length of the dam 628 (the distance from the inner wall surface 626a to the distal end on the outer wall surface 626b side) may be such that the film-forming resin solution can be spirally turned in the liquid storage portion 626 .

The length of the gap between the tip end of the dam 628 and the outer wall surface 626b of the liquid reservoir 626 is set such that the film forming resin solution flowing through the spiral flow path 626c is a length falling down from the outer wall surface 626b side .

As shown in Fig. 42, a slit portion 626d may be formed in the liquid storage portion 626 in the vicinity of the negative portion 627. By forming the slit portion 626d to give flow resistance, uniformity in the circumferential direction in discharging the film-forming resin solution is improved.

The negative portion 627 is a portion formed in the liquid storage portion 626 to form a film-forming resin solution stored in the form of an annular ring in a concentric cylindrical form with the support.

The width (distance between the inner wall and the outer wall) of the negative portion 627 can be appropriately set in accordance with the thickness of the porous film layer to be formed and the desired adhering condition.

In the spinning of the hollow fiber membrane by the spinning nozzle 62, a hollow support is fed from the support feed opening 623a to the support passage 623, and a device for feeding a film-forming resin solution in a fixed amount (for example, The film forming resin solution is supplied from the resin supply port 624a to the resin flow path 624 by a positive displacement pump such as a pump.

In the resin flow channel 624, the film-forming resin solution flowing through the inlet portion 625 is supplied to the liquid storage portion 626, and is swirled in the spiral shape in the liquid storage portion 626 by the branching and merging means The branching and merging are repeated so as to be separated from the inner wall surface 626a of the liquid reservoir 626 and the outer wall surface 626b so as to flow downward from the outer wall surface 626b of the dam reservoir 628, The confluent boundary of the forming resin solution does not form along the straight line passing through the central axis of the liquid storage portion 626 but is stored in the form of an annular circular ring and flows to the negative portion 627. The film-forming resin solution stored by the liquid storage portion 626 is formed into a concentric cylindrical shape through the negative portion 627 and discharged from the discharge port 624b and simultaneously discharged from the support outlet 623b Is applied to the outside of the derived support.

Thereafter, for example, in a container for bringing a film containing a water-containing gas into contact with the film-forming resin solution, the film-forming resin solution is allowed to pass through a coagulation bath in which the film-forming resin solution is brought into contact with the coagulating solution, , Or drying or the like to obtain a hollow fiber membrane.

The use of the spinning nozzles 11, 21, 31, 41, 51, 61, or 62 described above makes it possible to evenly form the film-forming resin solution in the circumferential direction even when the spinning speed is increased, It is possible to suppress the occurrence of cracks in the resultant hollow fiber membrane.

The hollow fiber spinning nozzle of the first embodiment of the present invention is not limited to the spinneret 11.

For example, the spinning nozzle 11 has a structure in which cylindrical porous elements 131 and 132 are provided in the first liquid storage part 118 or the second liquid storage part 121, The shape is not limited to a cylindrical shape. For example, a disk-shaped porous element may be provided on the slit portion 118b of the first liquid storage portion 118 and the slit portion 121b of the second liquid storage portion 121, The film-forming resin solution may pass from the outer peripheral surface to the inner peripheral surface of the porous element.

The hollow fiber spinning nozzle of the present invention has a composite portion inside the nozzle and the spinneret 11 has a composite portion 120 formed of the first and second cylindrical portions 119 and 123. However, Forming resin solution for forming two or more porous film layers may be separately discharged in a cylindrical shape and laminated on the outside of the nozzle and applied to the outside of the support. Specifically, the hollow fiber membrane spinning nozzle 12 (hereinafter referred to as " spinning nozzle 12 ") illustrated in Fig. 4 may be used. In the spinning nozzle 12, the same parts as those of the spinning nozzle 11 are denoted by the same reference numerals and description thereof is omitted.

The spinning nozzle 12 has a first nozzle 111, a second nozzle 112A, and a third nozzle 113A, and the first film-forming resin solution flowing from the first liquid storage portion 118 The first film forming resin solution flowing from the second liquid storing portion 121 is supplied to the support tube 114 in the form of a concentric circle with the support tube 114. The first tube- And has a second negative portion 122A which is shaped like a cylindrical shape. The first film-forming resin solution is supplied from the resin supply port 115a to the resin flow path 115 and discharged from the discharge port 115b after being formed in the first cylindrical portion 119A. The second film-forming resin solution is supplied from the resin supply port 116a to the resin flow path 116 and is discharged from the discharge port 116b after being formed in the second negative section 122A. The first film-forming resin solution and the second film-forming resin solution respectively discharged from the discharge ports 115b and 116b are laminated and synthesized outside the nozzle and applied to the outside of the support derived from the support outlet 114b.

The spinning nozzle 11 had the porous elements 131 and 132 through which the film-forming resin solution passed from the outer circumferential surface to the inner circumferential surface. The porous element in the hollow fiber spinning nozzle of the present invention, however, Anything that passes from this side is acceptable. For example, the hollow fiber membrane spinning nozzle 13 (hereinafter referred to as " spinning nozzle 13 ") illustrated in Fig. 5 may be used. The spinning nozzle 13 is a nozzle for spinning a hollow fiber membrane having a single-layer porous film layer.

The spinning nozzle 13 has a first nozzle 141 and a second nozzle 142 and includes a support passage 143 through which a hollow support is passed and a support member 143 through which a film- And a resin flow path 144. The resin flow path 144 includes an introduction part 145 for introducing the film-forming resin solution, a solution storage part 146 for storing the solution in the form of an annular circular ring in section, Forming resin solution flowing from the support passage 143 through the support passage 143. The support member 143 has a cylindrical portion 147 formed concentrically with the support body. In addition, inside the liquid storage portion 146, there is provided a porous element 151 through which the film-forming resin solution passes from the inner circumferential surface to the outer circumferential surface. As the porous element 151, the same ones as those exemplified in the porous element 131 can be used.

The film-forming resin solution in the spinning nozzle 13 is supplied from the resin supply port 144a to the resin flow path 144 and is supplied to the inside of the porous element 151 in the liquid storage part 146 And flows in an arc shape branched on both sides and joined on the opposite side. The film-forming resin solution passes through the porous element 151 from the inner circumferential surface toward the outer circumferential surface and is discharged from the discharge port 144b into a cylindrical shape at the cylindrical portion 147. At the same time, And is applied to the outside of the support. As described above, even if the porous element 151 through which the film-forming resin solution passes from the inner peripheral surface toward the outer peripheral surface is provided, the occurrence of cracks in the obtained hollow fiber membrane can be suppressed.

The hollow fiber spinning nozzle of the second embodiment of the present invention is not limited to the spinning nozzle 21 described above. For example, instead of the liquid storage portion 217 of the spinning nozzle 21, as shown in Fig. 14, an annular ring-shaped ring portion 217b and an annular ring portion 217b formed to be recessed outward from the ring portion 217b A first containing chamber 217C having six outer peripheral portions 217c and a second liquid storing chamber having an annular portion and six outer peripheral portions in the same manner and six feeding passages 217a are provided in portions of the outer peripheral portions 217c, Or a hollow fiber spinning nozzle having a liquid storage portion provided with a liquid storage portion.

Instead of the liquid storage portion 217 of the spinning nozzle 21, as shown in Fig. 15, a first liquid storage chamber 217D having an annular circular section and no outer peripheral portion, and a second liquid storage chamber having the same shape Or a hollow fiber spinning nozzle having a depressed portion provided with two or more supply paths 217a to follow the outer wall.

Further, the outer peripheral portion 217c of the first liquid storage chamber 217A may not be formed in a step shape, and the bottom surface may be constant as in the second liquid storage portion 217B.

The liquid storage portion 217 of the spinning nozzle 21 is divided into two liquid storage chambers. However, in the hollow fiber spinning nozzle of the present invention, the liquid storage portion may be divided into three or more empty chambers. The liquid storage portion in this case communicates with two or more supply passages provided so as to follow the outer wall, respectively.

The hollow fiber spinning nozzle of the present invention may be a nozzle for spinning a porous hollow fiber membrane having a multilayer porous membrane layer. For example, the film-forming resin solution having two cylindrical resin flow paths, each having a liquid reservoir portion and a hollow portion, such as the spinning nozzle 21, Or a hollow fiber spinning nozzle provided outside the support of the shape.

In this case, a composite portion may be provided in which the film-forming resin solution is laminated and compounded inside the spinning nozzle, or each of the film-forming resin solutions may be laminated and mixed on the outside of the nozzle to be provided outside the support.

The hollow fiber spinning nozzle according to the third aspect of the present invention is not limited to the spinning nozzle 31 as long as a filling layer filled with particles is formed inside the liquid storing portion. For example, the hollow fiber membrane spinning nozzle 32 (hereinafter referred to as " spinning nozzle 32 ") illustrated in Figs. 19 and 20 may be used.

The spinning nozzle 32 has a first nozzle 331 and a second nozzle 332 and is provided therein with a support passage 333 through which a hollow support is passed and a film forming resin solution And a resin flow path 334 for flowing the resin. The resin flow path 334 includes an introduction portion 335 into which the film-forming resin solution is introduced, a liquid storage portion 336 in which the film-forming resin solution is made into an annular circular shape and a liquid is stored, As shown in Fig. The liquid reservoir 336 has a circular cross-sectional shape in the horizontal direction and a semicircular cross-sectional shape in the vertical direction. A filling layer 340 filled with spherical particles 341 having a diameter substantially equal to the height of the liquid storage portion 336 is formed in the liquid storage portion 336. [

The negative electrode 337 is formed to have a cylindrical shape concentric with the supporter that allows the film-forming resin solution flowing from the liquid reservoir 336 to pass through the supporter passage 333.

In the hollow fiber membrane spinning nozzle according to the third aspect of the present invention, the filling layer may not be formed from the bottom of the hollow portion. For example, a disc supporting body through which a film-like wire mesh or a film-forming resin solution such as a filter passes is provided at a predetermined height in the inside of the embedding portion. On the disc supporting portion inside the embedding portion, Or a packed layer may be formed by filling the particles.

The hollow fiber spinning nozzle of the present invention may be a nozzle for spinning a porous hollow fiber membrane having a multi-layered porous membrane layer. For example, two resin flow paths, each having a liquid storage portion and a negative portion, such as the spinning nozzle 31, and a filling layer filled with particles are formed in each of the liquid storage portions. In each of the cylindrical portions, A hollow fiber membrane spinning nozzle may be used in which a film-forming resin solution which has been adhered and laminated in a concentric circular shape is applied to the outside of the hollow support body. In this case, a composite part may be provided inside the spinning nozzle to laminate and composite film-forming resin solutions formed by the respective negative parts, so that the film-forming resin solution is laminated and mixed on the outside of the nozzle to be provided outside the support You can.

The hollow fiber spinning nozzle according to the fourth aspect of the present invention is not limited to the spinneret 41. For example, although the liquid storage portion of the spinning nozzle 41 has four stages, the liquid storage portion may have two or three stages or five or more stages.

Further, although the resin supply portions are provided at equal intervals so as to be shifted by 225 degrees in the counterclockwise direction from each other along the circumferential direction of the liquid storage portion 416, the position where the resin supply portion is formed is not particularly limited. For example, the first resin supply portion 416a, the second resin supply portion 416b, and the third resin supply portion 416c of the spinning nozzle 41 are rotated in the counterclockwise direction 135 Or may be formed so as to be shifted by degrees.

In addition, the hollow fiber spinning nozzle of the present invention may be a nozzle that emits a porous hollow fiber membrane in which a porous membrane layer formed by another film-forming resin solution is laminated. For example, the above-mentioned film-forming resin solutions having two kinds of resin flow paths having the liquid storage portion and the shaping portion and having different types of cylindrically shaped resin solutions in the respective resin flow paths are stacked and laminated in a concentric circular shape, Or a hollow fiber membrane spinning nozzle provided outside the support body. In this case, a composite part may be provided on the downstream side of each of the lowermost bulging portions of the two resin flow paths, in which a film-forming resin solution flowing through each resin flow path is laminated and compounded. The resin solution may be laminated and combined to be provided on the outer side of the support.

The hollow fiber spinning nozzle according to the fifth aspect of the present invention is not limited to the spinning nozzle 51 described above. For example, in the spinning nozzle 51, the number of the annular flow path portions of the meandering portion 518 is five, but the number is not limited to five.

The number of the annular flow path portions of the meandering portion 518 may be two or more.

The meandering portion 518 of the spinning nozzle 51 is a portion that meanders the film-forming resin solution flowing in from the liquid storage portion 516 upward and downward toward the center direction. However, The spinning nozzle is not limited to this shape as long as it has a meandering portion.

For example, the hollow fiber membrane spinning nozzle 52 (hereinafter referred to as " spinning nozzle 52 ") illustrated in Fig. 35 may be used. The spinning nozzle 52 has a first nozzle 521a, a second nozzle 521b, a third nozzle 522a and a fourth nozzle 522b. The spinning nozzle 52 has a support passage 523), and a resin flow path (524) for flowing a film-forming resin solution for forming a porous film layer. The resin flow path 524 includes an introduction portion 525 into which the film-forming resin solution is introduced, a liquid storage portion 526 that stores the solution in the form of an annular circular ring in the form of a film-forming resin solution, And has a negative-shaped portion 527 which is formed. The spinning nozzle 52 has a meandering portion 528 between the liquid storage portion 526 and the tubular portion 527 for vertically skewing the film-forming resin solution while keeping it in an annular circular shape.

As shown in Fig. 35, the meandering portion 528 of the spinning nozzle 52 is configured to flow the film-forming resin solution flowing in from the liquid storage portion 526 in a vertical direction .

The hollow fiber spinning nozzle of the present invention may be a nozzle for spinning a porous hollow fiber membrane having a multi-layered porous membrane layer. For example, two liquid resin flow paths 715 and 722 having liquid reservoirs 717 and 724 such as a spinning nozzle 71, negative portions 728 and 718, and serpentine portions 719 and 726, The hollow fiber membrane spinning nozzle may be a hollow fiber membrane spinning nozzle which laminated and laminated the film-forming resin solutions formed by the hollow sections 728 and 718 of the resin flow paths 715 and 722 in a concentric circular shape and attached to the outside of the hollow support body. In this case, a composite portion 730 in which the film-forming resin solutions are laminated and compounded may be provided inside the spinning nozzle, and the film-forming resin solutions may be stacked on the outside of the nozzles to be provided outside the support .

The two dams 618 and the dams 619 are provided in a spiral shape in the liquid storage portion 616 of the spinning nozzle 61 described above. However, even if only one dike is provided in a spiral shape do. For example, as shown in FIG. 40, a single dam 618A extending from the lower wall surface toward the upper wall surface may be provided in the liquid storage portion 616 in a spiral shape. Even in such a form, the film-forming resin solution circulates in the liquid storage portion 616 so as to overflow the dike 618A while swirling in the form of a spiral, repeating fine branching and merging, It is considered that the confluent boundary of the film-forming resin solution between the inner wall surface and the outer wall surface is inhibited from being formed along a straight line passing through the central axis of the liquid reservoir 616. As a result, it is possible to suppress the formation of a starting point of a crack along the axial direction in the porous film layer, and it is possible to suppress the occurrence of cracks in the obtained hollow fiber membrane.

The hollow fiber spinning nozzle according to the sixth aspect of the present invention is not limited to the spinning nozzle (61 or 62). For example, the hollow fiber spinning nozzle of the present invention may be a nozzle that emits a porous hollow fiber membrane having a multi-layered porous membrane layer. Specifically, it is preferable that two resin flow paths having a liquid storing portion and a forming portion such as the spinning nozzle 61 or 62 are provided and each of these liquid storing portions is regulated so as to turn the flow of the film- And the hollow fiber membrane spinning nozzle may be a hollow fiber membrane spinning nozzle which is provided on the outer side of the hollow support body by stacking and laminating the film-forming resin solution stored in the solution storage section in a concentric cylindrical shape. In this case, a composite part for laminating and composing a film-forming resin solution stored in each liquid storage part may be provided in the spinning nozzle, or a film-forming resin solution may be laminated on the outside of the nozzle, .

The spinneret of the present invention may be a spinneret having a support passage for passing a support at the center thereof, or a spinneret for spinning a porous hollow fiber membrane having no hollow support.

By passing a support or a core liquid or the like through the support passage, a hollow hollow fiber membrane is obtained. It is preferable that the support passage is passed through the support passage.

In the case where the spinning nozzle of the present invention is a spinning nozzle that emits a porous hollow fiber membrane having no hollow support, a core liquid or the like is passed through the support channel, and solidification and washing are performed to produce a porous hollow fiber membrane having a hollow porous membrane can do. As the core liquid, those having desired coagulation power may be appropriately selected. As the core liquid, for example, water, a non-solvent such as glycerin or ethylene glycol may be used alone or as a mixture, a mixed solution with a solvent, or a combination of a plurality of these, or a soluble polymer such as polyvinyl pyrrolidone .

The spinning nozzle of the present invention preferably has only one support passage.

<Manufacturing Method of Hollow Fiber Membrane>

The method for producing a hollow fiber membrane having a hollow porous membrane layer of the present invention includes a spinning process of spinning a hollow fiber membrane from a film-forming resin solution, a coagulation process of coagulating the spinning hollow fiber membrane by a coagulating solution, A desolvating process for removing the solvent from the hollow fiber membrane, a decomposition and cleaning process for decomposing and removing the additive contained in the hollow fiber membrane from which the solvent has been removed by cleaning, a drying process for drying the hollow fiber membrane after the cleaning, It is preferable that the spinning step of spinning the hollow fiber membrane from the film-forming resin solution has a spinning step of spinning up the hollow fiber membrane and spinning the hollow fiber membrane from the film-forming resin solution by the hollow fiber spinning nozzle of the present invention .

<< Radiation Process >>

In the method for producing a hollow fiber membrane of the present invention, the above-mentioned film-forming resin solution is first prepared. The spinning nozzle of the present invention used in the method for producing a hollow fiber membrane of the present invention has a support passage for allowing a hollow support to pass therethrough and a resin flow passage for flowing a film-forming resin solution for forming a porous film layer. In the spinning nozzle, a hollow support is fed from the support feed port and is led out from the support outlet, and the film-forming resin solution is fed from the resin feed port and discharged in a cylindrical shape around the support from the ejection port. In the spinning of the hollow fiber membrane by the spinning nozzle of the present invention, the film-forming resin solution discharged from the discharge port of the spinning nozzle is given to the outside of the hollow support which is simultaneously led out from the support outlet.

<< Coagulation process >>

Contacting the coagulation liquid in the coagulation bath with the film-forming resin solution discharged from the spinning nozzle to coagulate the film-forming resin solution to replace the solvent in the film-forming resin solution with non-solvent, To obtain a hollow fiber membrane precursor having a hollow porous membrane layer.

(Air-wet spinning) is performed even after the hollow fiber membrane precursor is discharged from the spinneret until the coagulating bath containing the coagulating solution is introduced (dry-wet spinning) Radiation).

The film-forming resin solution used in the present invention is a solution (a film-forming solution) obtained by dissolving a film-forming resin and an additive (pore-forming agent) for the purpose of phase separation control in an organic solvent for both solvents. The coagulating solution may be water, ethanol, methanol or the like, or a mixture thereof. Particularly, a mixed solution of a solvent and water used in the stock solution is preferable from the viewpoints of safety and operation management.

<< Desolvation Process >>

As described above, since a large amount of a solvent or the like remains in the hollow fiber membrane precursor solidified by the coagulation step, a step of removing the solvent or the like remaining in the hollow fiber membrane precursor is performed (desolvation process).

In the desolvation step, the hollow fiber membrane precursor having the hollow porous membrane layer is contacted with hot water in the desolvation tank to remove the solvent. It is effective to set the temperature of the hot water as high as possible within a range in which the hollow fiber membrane precursors are not fused with each other. Therefore, the temperature of the hot water is preferably 20 to 100 캜, more preferably 50 to 100 캜.

<< Decomposition and Cleaning Process >>

The decomposition and washing step is a step of decomposing an additive (pore-forming agent) in the hollow fiber membrane precursor by hypochlorous acid or the like and removing it by subsequent washing.

In the step of decomposition and washing, the hollow fiber membrane precursor after the desolvation step is immersed in an aqueous solution of sodium hypochlorite, which is an oxidizing agent, and the additives (openers) are decomposed by oxidative decomposition in a decomposition bath. Thereafter, the additive (opener) is washed with hot water in the high-speed cleaning tank. The decomposition and cleaning step is carried out one time or two or more times so as to reach the desired level of the additive (open reduction agent) in the hollow fiber membrane precursor.

<< Drying Process and Winding Process >>

In the drying process, the hollow fiber membrane subjected to the decomposition and washing process is dried.

The method of the drying step is not particularly limited, and the hollow fiber membrane may be introduced into a dryer 77 such as a hot air dryer.

For example, the hollow fiber membrane after the decomposition and washing process is dried at a temperature of 60 ° C or higher for less than 24 hours in total for a time period of 1 minute or more, and then wound on a winding machine such as bobbin or failure.

The hollow fiber membrane of the present invention and the method of manufacturing the hollow fiber membrane of the present invention using the spinneret can produce a hollow fiber membrane in which cracking along the axial direction is less likely to occur even when the spinning speed is increased. The ease of occurrence of film cracks can be confirmed by a film cracking confirmation test described later.

The spinning nozzle of the present invention or the hollow fiber membrane produced by the production method of the present invention is a hollow fiber membrane having a hollow porous film layer and has a hollow portion at the center thereof. It is preferable that the hollow fiber membrane has only one hollow portion.

The outer diameter d of the hollow fiber membrane refers to the diameter of the outermost periphery of the membrane in the annular cross section of the hollow fiber membrane. The inner diameter dh of the hollow fiber membrane refers to the diameter of the inner surface of the support on the annular cross section of the hollow fiber membrane.

(Outer diameter d of the hollow fiber membrane)

The outer diameter d of the hollow fiber membrane was measured by the following method.

The sample to be measured was cut to about 10 cm, and several pieces were bundled, and the whole was covered with a polyurethane resin. The polyurethane resin was also allowed to penetrate into the hollow portion in the support.

After the curing of the polyurethane resin, a flake having a thickness of 0.5 mm was sampled using a razor blade.

Next, the annular section of the sampled hollow fiber membrane was observed with an objective lens 100 times using a projector (PROFILE PROJECTOR V-12 made by Nikon Corporation).

Marks (lines) were aligned with the positions of the outer surface of the hollow porous film in the X and Y directions, and the coordinates were read to calculate the outer diameter d. This was measured three times to obtain an average value of the outer diameter d.

The inner diameter dh of the hollow fiber membrane was measured by the following method.

The sample to be measured was sampled in the same manner as the sample in which the outer diameter d was measured.

Next, the annular section of the sampled hollow fiber membrane was observed with an objective lens 100 times using a projector (PROFILE PROJECTOR V-12 made by Nikon Corporation).

Marks (lines) were fitted to the positions of the inner surface of the support in the X and Y directions of the hollow fiber membrane being observed, and the coordinates were read, and the inner diameter dh was calculated therefrom. This was measured three times to obtain an average value of the inner diameter dh.

Normally, the hollow fiber membrane permeates the object to be filtered from the outer surface of the membrane to the inner surface of the membrane, but when the value of d / dh becomes large, the diameter d, which is a parameter used in the estimation of the filtration surface of the hollow fiber membrane, Since the inner diameter dh which is a parameter to be used in estimating the flow resistance of the fluid in the hollow portion after passing through the desert surface is small or the outer diameter d is larger than the inner diameter dh, the flow resistance when the fluid after filtration flows through the hollow portion , The effective use of the hollow fiber membrane becomes difficult, the coagulation delay of the film-forming resin solution occurs, and a desired film structure is not obtained, or the film-forming resin solution excessively enters the inside of the support, And so on.

If the value of d / dh becomes smaller, the difference between the outer diameter d and the inner diameter dh of the hollow fiber membrane becomes smaller, and the film thickness of the hollow fiber becomes thinner.

The preferable range of d / dh is 1.3 to 5.0, more preferably 1.4 to 3.5, and most preferably 1.5 to 2.0.

The outer diameter d of the hollow fiber membrane is preferably 0.5 mm or more and 5.0 mm or less. When the outer diameter d of the hollow fiber membrane is smaller than 0.5 mm, it becomes difficult to manufacture the hollow reinforcing support. If the outer diameter d of the hollow fiber membrane exceeds 5 mm, the efficiency of collecting the membrane elements is lowered and a desired throughput can not be obtained. In addition, the possibility of occurrence of defective process passability such as turning due to a guide in the hollow fiber membrane production process .

(Example)

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited thereto.

(Film cracking confirmation test)

The hollow fiber membrane was sandwiched between the heads of a digital micrometer (Mitutoyo MDC-25MJ) such that the measurement direction of the micrometer was the diameter direction of the membrane, and the outer diameter of the hollow fiber membrane measured by the projector was set to zero, The spindle was rotated so that the indicated value of the meter was negative and the film was compressed and deformed until the absolute value of the indication of the micrometer reached the value of the hollow portion diameter of the hollow fiber membrane measured by the projector, And an indication of the micrometer at the time of cracking was recorded.

When the film crack was not observed, once the micrometer was opened, the film was rotated by 45 °, and then the film was again compressed and deformed to confirm the occurrence of cracks. The measurement samples were about 3 cm in length.

As an index of the cracking property, a crack was observed before the absolute value of the indication of the micrometer reached the diameter of the hollow portion of the film, and a crack was observed.

[Example 1]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of the International Publication No. 2009/142279.

(Preparation of hollow fiber membrane)

(Manufactured by Nippon Shokubai Co., Ltd. under the trade name of K-2), polyvinylidene fluoride A (trade name: Kana 301F), polyvinylidene fluoride C (trade name: Kana 9000HD), polyvinyl pyrrolidone 79) and N, N-dimethylacetamide (DMAc) (manufactured by Samsung Fine Chemical Co., Ltd.) were mixed in the mass ratios shown in Table 1 to prepare film-forming resin solutions (3 and 4).

Using the hollow fiber spinning nozzle 11 in which the porous element (sintered metal element ESP-20-40-2-70 made by SMC Co., Ltd., length 13 mm) was disposed in each liquid storage portion, the spinning nozzle was maintained at 32 캜 The hollow knit braid support was supplied from the support feed port 114a and traveled at a running speed of 10 m / min. As a first film-forming resin solution, a film-forming resin solution (4) was supplied from a resin supply port (115a), and as a second film-forming resin solution, a film-forming resin solution (3) 116a. The two kinds of film-forming resin solutions were laminated and compounded in the spinning nozzle, and after discharging from the nozzle, they were coated and laminated on the hollow knit braid support, and passed through an air gap of 62 mm. Except for the above, a hollow fiber membrane was prepared in the same manner as in Example 4 of the brochure WO 2009/142279.

A porous element having a pore diameter of 70 mu m was disposed in each solution reservoir of the hollow fiber membrane. The number of the calculated joins after passing through the porous element disposed in each liquid storage portion was 2,872.

The outer diameter d of the obtained hollow fiber membrane was 2.75 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.83.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 2]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of the International Publication No. 2009/142279.

(Preparation of hollow fiber membrane)

A hollow fiber membrane was prepared in the same manner as in Example 1 except that a porous element (sintered metal element ESP-20-40-2-120, manufactured by SMC, length: 13 mm) having a pore diameter of 120 탆 was disposed in each of the solution reservoirs .

The number of the calculated joins of the porous elements arranged in each solution reservoir of the hollow fiber membrane was 1676.

The outer diameter d of the obtained hollow fiber membrane was 2.75 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.83.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 3]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of the International Publication No. 2009/142279.

(Preparation of hollow fiber membrane)

The same procedure as in Example 1 was carried out except that the porous filter element of each liquid storage portion had a nominal filtration accuracy of 150 mu m (sintered wire mesh Fujiro (registered trademark) manufactured by Fuji Filter Co., Ltd., outer diameter 14 mm, inner diameter 11 mm, length 13 mm) To prepare a hollow fiber membrane.

The number of the calculated joins after passage of the porous element disposed in each solution reservoir of the hollow fiber membrane was 922.

The outer diameter d of the obtained hollow fiber membrane was 2.75 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.83.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 4]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of International Publication No. 2009/142279 except that the heating die temperature was 190 占 폚 and the outside diameter of the support was 2.55 mm.

(Preparation of hollow fiber membrane)

(Trade name: Kana 301F), polyvinyl pyrrolidone (Nihon Shokubai Co., Ltd., trade name: K-79) and N, N-dimethylacetamide (DMAc) Ltd.) were mixed in a mass ratio shown in Table 1 to prepare a film-forming resin solution (5).

A porous element (sintered metal element ESP-14-40-2-70 made by SMC, length: 13 mm) having a pore diameter of 70 탆 was disposed in the liquid storage part 121, and the first film- , The resin supply port 115a was removed and the film-forming resin solution 5 was supplied as the second film-forming resin solution from the resin supply port 116a, .

The number of the calculated joins after passing through the porous element disposed in the liquid storage portion of the hollow fiber membrane was 1,795.

The outer diameter d of the obtained hollow fiber membrane was 2.75 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.83.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 5]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 1. [

(Preparation of hollow fiber membrane)

A hollow fiber membrane (a sintered metal element ESP-14-40-2-120 manufactured by SMC Corporation, length 13 mm) having a pore diameter of 120 탆 was disposed in the liquid storage portion 121, and a hollow fiber membrane was prepared in the same manner as in Example 4 .

The number of the calculated joins after passing through the porous element disposed in the liquid storage portion of the hollow fiber membrane was 1047. [

The outer diameter d of the obtained hollow fiber membrane was 2.75 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.83.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 6]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 1. [

(Preparation of hollow fiber membrane)

(4 mm in outer diameter, 11 mm in inner diameter, and 13 mm in length) of porous element having hole diameter of 150 탆 (sintered wire mesh Fujiro (registered trademark) manufactured by Fuji Filter Co., Ltd.) To prepare a hollow fiber membrane.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 7]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4. [

(Preparation of hollow fiber membrane)

(Manufactured by Nippon Shokubai Co., Ltd., trade name: K-2), polyvinylidene fluoride B (trade name: Kana 9000 LD), polyvinyl pyrrolidone 79) and N, N-dimethylacetamide (DMAc) (manufactured by Samsung Fine Chemicals Co., Ltd.) were mixed in the mass ratios shown in Table 1 to prepare film-forming resin solutions (5) and (6).

A hollow fiber membrane was prepared in the same manner as in Example 4 except that a porous element (sintered metal element ESP-20-40-2-70 manufactured by SMC, length 13 mm) having a pore diameter of 70 μm was disposed in each of the liquid storage portions .

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 8]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4. [

(Preparation of hollow fiber membrane)

A hollow fiber membrane was prepared in the same manner as in Example 7 except that a porous element (sintered metal element ESP-20-40-2-120 manufactured by SMC, length: 13 mm) having a pore diameter of 120 탆 was disposed in each of the liquid storage portions .

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 9]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4. [

(Preparation of hollow fiber membrane)

Except that a porous element (sintered wire mesh Fujiro (registered trademark) manufactured by Fuji Filter Co., Ltd., outer diameter: 14 mm, inner diameter: 11 mm, length: 13 mm) having a hole diameter of 150 μm was disposed in each of the liquid storage portions To prepare a hollow fiber membrane.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 10]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of the International Publication No. 2009/142279.

(Preparation of hollow fiber membrane)

A porous element (sintered metal element ESP-20-40-2-120, manufactured by SMC Co., Ltd., having a length of 13 mm) having a pore size of 120 탆 was disposed in the liquid storage portion 118a, A porous element having an inner diameter of 26 mm and a length of 13 mm and having a length of 6.5 mm and piercing 72 holes of 0.5 mm in diameter at an interval of 5 degrees from the outer periphery of the cylinder toward the inner periphery of the cylinder was arranged A hollow fiber membrane was prepared in the same manner as in Example 1.

The number of the calculated joins after passage of the porous element disposed in the inner layer liquid storage portion 118 of the hollow fiber membrane was 1676 and the number of the calculated joins after passing through the porous element disposed in the liquid storage portion 121 of the outer layer was 72. [

The outer diameter d of the obtained hollow fiber membrane was 2.75 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.83.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Comparative Example 1]

A porous hollow fiber membrane was obtained by spinning in the same manner as in Example 1, except that the porous element of Example 1 was not disposed at either of the liquid storage portions 118a and 121a.

The outer diameter d of the obtained hollow fiber membrane was 2.75 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.83.

As a result of the confirmation of the film cracking property of the obtained porous hollow fiber membrane, cracking of the membrane was observed.

[Comparative Example 2]

A porous hollow fiber membrane was obtained by spinning in the same manner as in Example 1, except that the porous element of Example 1 was not disposed in the liquid storage portion 118a.

As a result of the confirmation of the film cracking property of the obtained porous hollow fiber membrane, cracking of the membrane was observed.

[Comparative Example 3]

A porous hollow fiber membrane was obtained by spinning in the same manner as in Example 1 except that the porous element of Example 1 was not disposed in the liquid storage portion 121a.

As a result of the confirmation of the film cracking property of the obtained porous hollow fiber membrane, cracking of the membrane was observed.

[Comparative Example 4]

A hole having a diameter of 0.5 mm was formed in the liquid storage portion 121a of Example 10 from a cylindrical outer periphery toward a cylindrical inner periphery at a position of 6.5 mm in length with a cylindrical shape having an outer diameter of 20 mm, , And a perforated porous element was disposed at 36 places in the hollow fiber membrane.

The number of the calculated joins after passage of the porous element disposed in the inner layer liquid storage portion 118 of the hollow fiber membrane was 1676 and the number of the calculated joins after passing through the porous element disposed in the liquid storage portion 121 of the outer layer was 36. [

The outer diameter d of the obtained hollow fiber membrane was 2.75 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.83.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, a film crack was observed.

[Example 11]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of International Publication No. 2009/142279 except that the heating die temperature was 190 캜 and the outside diameter of the support was 2.55 mm.

(Preparation of hollow fiber membrane)

(Trade name: Kana 301F), polyvinyl pyrrolidone (Nihon Shokubai Co., Ltd., trade name: K-79) and N, N-dimethylacetamide (DMAc) Ltd.) were mixed in a mass ratio shown in Table 1 to prepare a film-forming resin solution (5).

Using the hollow fiber spinning nozzle having twelve outer peripheral portions recessed toward the outer side in the liquid storage chamber, the hollow knitted braid support was supplied from the supporter supply port 214a while keeping the spinning nozzle at 32 ° C And traveled at a traveling speed of 2 m / minute. The film-forming resin solution 5 was supplied from the resin supply port 215a, discharged from the hollow fiber membrane spinning nozzle, and then coated and laminated with the hollow knit braid support, and passed through an air gap of 42 mm. Except for the above, a hollow fiber membrane was prepared in the same manner as in Example 4 of the brochure WO 2009/142279.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 12]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of International Publication No. 2009/142279 except that the heating die temperature was 190 占 폚 and the outside diameter of the support was 2.55 mm.

(Preparation of hollow fiber membrane)

(Trade name: Kana 301F), polyvinyl pyrrolidone (Nihon Shokubai Co., Ltd., trade name: K-79) and N, N-dimethylacetamide (DMAc) Ltd.) were mixed in a mass ratio shown in Table 1 to prepare a film-forming resin solution (5).

Using the hollow fiber spinning nozzle in which seven steel balls having a diameter of 2.79 mm were placed in the liquid storage portion, the hollow knit braid support was supplied from the support feed port 313a while the spinning nozzle was kept at 32 占 폚 , Running at a running speed of 4m per minute. The film-forming resin solution 5 was supplied from a resin supply port 314a, discharged from the hollow fiber membrane spinning nozzle, and then coated and laminated with the hollow knit braid support, and passed through an air gap of 42 mm. Except for the above, a hollow fiber membrane was prepared in the same manner as in Example 4 of the brochure WO 2009/142279.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 13]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of International Publication No. 2009/142279 except that the heating die temperature was 190 占 폚 and the outside diameter of the support was 2.55 mm.

(Preparation of hollow fiber membrane)

A hollow fiber membrane was prepared in the same manner as in Example 12, except that 300 steel balls having a diameter of 1.51 mm were arranged in the solution reservoir.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Comparative Example 5]

A hollow fiber membrane was obtained by spinning in the same manner as in Example 12, except that a steel ball was not filled in the solution reservoir using the support thus prepared in the same manner as in Example 12. [

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, a film crack was observed.

[Example 14]

A hollow knit braid support was prepared in the same manner as in Example 4 of International Publication No. 2009/142279 except that the heating die temperature was 190 占 폚 and the outside diameter of the support was 2.55 mm.

(Preparation of hollow fiber membrane)

(Manufactured by Nippon Shokubai Co., Ltd., trade name: K-2), polyvinylidene fluoride B (trade name: Kana 9000 LD), polyvinyl pyrrolidone 79) and N, N-dimethylacetamide (DMAc) (manufactured by Samsung Fine Chemicals Co., Ltd.) were mixed in the mass ratios shown in Table 1 to prepare film-forming resin solutions (5) and (6).

The liquid storage portion is arranged in two stages in the resin flow path of the film forming resin solution 6 and the liquid storage portion is arranged in two stages in the resin flow path of the film forming resin solution 5 and the hollow portion A desert spinning nozzle 41 was used. The hollow knit braid support was fed from a support feed port at a running speed of 10 m per minute and the film forming resin solutions 5 and 6 were fed into a resin feed port Respectively. The two kinds of film-forming resin solutions (5) and (6) were laminated and mixed in the inside of a nozzle, discharged from a nozzle, coated and laminated with the hollow knit braid support, and passed through an air gap of 42 mm. Except for the above, a hollow fiber membrane was prepared in the same manner as in Example 4 of the brochure WO 2009/142279.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Comparative Example 6]

A hollow fiber membrane was obtained by spinning in the same manner as in Example 14, except that the liquid storage portions in Example 14 were used one by one and a nozzle in which the position of the resin supply portion was shifted by 180 degrees was used.

As a result of the confirmation of the film cracking property of the obtained porous hollow fiber membrane, cracking of the membrane was observed.

[Example 15]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of International Publication No. 2009/142279 except that the heating die temperature was 190 占 폚 and the outside diameter of the support was 2.55 mm.

(Preparation of hollow fiber membrane)

(Manufactured by Nippon Shokubai Co., Ltd., trade name: K-2), polyvinylidene fluoride B (trade name: Kana 9000 LD), polyvinyl pyrrolidone 79) and N, N-dimethylacetamide (DMAc) (manufactured by Samsung Fine Chemicals Co., Ltd.) were mixed in the mass ratios shown in Table 1 to prepare film-forming resin solutions (5) and (6).

44, the hollow knit braid support was fed from the support feed port 714a and traveled at a running speed of 10 m / min. As the film-forming resin solution of the inner layer, a film-forming resin solution (6) was supplied from the resin supply port (722a) of the inner layer and the film-forming resin solution (5) And supplied from the resin supply port 715a. Each of the film-forming resin solutions is guided to the respective liquid reservoirs 717 and 724, branched and joined together to form an annular circular shape, and the inner layer is meandering upward and downward and passes through the meandering portion 726 through a retention time of about 10 seconds And the outer layer was led to the negative portion 718 through the meandering portion 719 at a retention time of about 60 seconds while the outer layer was meandering up and down. Each of the film-forming resin solutions was laminated and mixed in a nozzle, discharged from a nozzle, coated and laminated with the hollow knit braid support, and passed through an air gap of 62 mm. Except for the above, a hollow fiber membrane was prepared in the same manner as in Example 4 of the brochure WO 2009/142279.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 16]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 15. [

(Preparation of hollow fiber membrane)

(Trade name: Kana 301F), polyvinyl pyrrolidone (Nihon Shokubai Co., Ltd., trade name: K-79) and N, N-dimethylacetamide (DMAc) Ltd.) were mixed in a mass ratio shown in Table 1 to prepare a film-forming resin solution (5).

Like in Example 1 except that the film-forming resin solution 5 was supplied from the resin supply port 514a and was led to the negative portion 517 through the meandering portion 518 through the residence time of about 10 seconds To prepare a hollow fiber membrane.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Comparative Example 7]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 15. [

(Preparation of hollow fiber membrane)

The film-forming resin solution (5) was prepared by mixing with the mass ratios shown in Table 1 in the same manner as in Example 16.

A hollow fiber membrane was produced in the same manner as in Example 2 except that the film-forming resin solution (5) was supplied from a resin feed port and was led to the negative portion through a retraction time of about 3 seconds.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, a film crack was observed.

[Example 17]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 4 of International Publication No. 2009/142279 except that the heating die temperature was 190 占 폚 and the outside diameter of the support was 2.55 mm.

(Preparation of hollow fiber membrane)

(Trade name: Kana 301F), polyvinyl pyrrolidone (Nihon Shokubai Co., Ltd., trade name: K-79) and N, N-dimethylacetamide (DMAc) Ltd.) were mixed in a mass ratio shown in Table 1 to prepare a film-forming resin solution (5).

A hollow spiral spinning nozzle was used in which a continuous spiral dike was arranged in the liquid reservoir to turn the spiral dike to 2.5 and the clearance between the dike tip and the top wall to be 0.1 mm. With the spinning nozzle kept at 32 ° C, the hollow knit braid support was fed from the support feed port and run at a traveling speed of 10 m / min. The film-forming resin solution (5) was supplied from a resin supply port, discharged from a nozzle, and then applied to and laminated on the hollow knit braid support, and passed through an air gap of 42 mm. Except for the above, a hollow fiber membrane was prepared in the same manner as in Example 4 of the brochure WO 2009/142279.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Example 18]

(Preparation of Support)

A hollow knit braid support was prepared in the same manner as in Example 1. [

(Preparation of hollow fiber membrane)

A film-forming resin solution (5) was prepared in the same manner as in Example 1.

A continuous spiral dike was arranged in the liquid reservoir to turn the spiral dike about 6 weeks. The tip of the dam was formed into a conical shape with an angle of 14 degrees so as to be smaller toward the discharge port, and the outer wall surface was formed into a conical shape with an angle of 10 degrees so as to decrease toward the discharge port. The hollow fiber spinning nozzle having a clearance of about 0.3 mm with respect to the outer wall surface at the end of the helix was used to run at a traveling speed of 5 m / min. A hollow fiber membrane was produced in the same manner as in Example 1 except for the above.

As a result of the confirmation of the film cracking property of the obtained hollow fiber membrane, no crack was observed.

[Comparative Example 8]

Except that the polyester had a fineness of 167 dtex, a number of filaments of 72, a number of bobbins of 3, a total fineness of 501 dtex, and an inner diameter of the heating die of 1.8 mm, the same procedure as in Example 4 of the International Patent Publication No. 2009/142279 Mm, and a support inner diameter of 1.5 mm.

The number of the calculated joins after passing through the porous elements arranged in the respective liquid storage portions was 922.

A porous hollow fiber membrane was obtained by spinning in the same manner as in Example 3 except that the amount of discharge was adjusted so as to obtain a desired outer diameter by changing the support.

The outer diameter d of the obtained hollow fiber membrane was 1.8 mm, the inner diameter dh was 1.5 mm, and the d / dh was 1.2.

The obtained porous hollow fiber membrane was flat and the membrane was crushed.

[Comparative Example 9]

A hollow knit braid support was prepared in the same manner as in Example 4 of the International Publication No. 2009/142279.

A porous hollow fiber membrane was obtained by spinning in the same manner as in Example 3 except that the discharge amount was adjusted so as to obtain a desired outer diameter.

The outer diameter d of the obtained hollow fiber membrane was 8.5 mm, the inner diameter dh was 1.5 mm, and the d / dh was 5.67.

The resultant porous hollow fiber membrane was found to have a hollow portion occluded by the excessive introduction of the film-forming resin into the hollow portion.

Table 2 shows the results of calculating the number of calculated combinations for Examples 1 to 5 and Example 10 and Comparative Example 1 and Comparative Example 4. As apparent from Table 2, in Examples 1 to 5 and Example 10 in which the number of calculated joins was more than 50, no cracks in the film were observed as a result of the confirmation of the film cracking property of the hollow fiber membrane obtained as described above. On the other hand, in Comparative Example 1 and Comparative Example 4 in which the number of calculated joins was less than 50, film cracking was observed as a result of the confirmation of the film cracking property of the hollow fiber membrane obtained as described above.

INDUSTRIAL APPLICABILITY The hollow fiber spinning nozzle and the method for producing a hollow fiber according to the present invention can be used in the field of water treatment and the like because a hollow fiber membrane with less cracking along the axial direction can be produced even if the spinning speed is increased.

11 to 13: hollow fiber spinning nozzle
111, 141: first nozzle
112, 112A, 142: a second nozzle
113, 113A: third nozzle
114, 143: support passage portion
115, 116 and 144:
117, 120, 145:
118: First solution storage part
119:
121: second solution storage part
122:
146:
147:
131, 132, 151: porous element
21: hollow fiber spinning nozzle
211: first nozzle
212: second nozzle
213: third nozzle
214: support passage
215: resin flow path
216:
217:
217A: first liquid storage chamber
217B: the second liquid storage chamber
217a: Supply path
218:
31, 32: hollow fiber spinning nozzle
311, 331: a first nozzle
312, 332: second nozzle
313, 333: support passage
314, 334:
315, 335:
316, 336:
317, 337:
320, 340: filling layer
321, 341: particles
41: hollow fiber spinning nozzle
411: first nozzle
412a: second nozzle
412b: third nozzle
412c: fourth nozzle
412d: fifth nozzle
413: Support passage
414:
415:
416:
416A: first liquid storage portion
416B: the second solution reservoir
416C: third solution storage part
416D: fourth solution reservoir
416a: first resin supply part
416b: second resin supply part
416c: third resin supply part
417:
417A:
417B:
417C: Part 3
417D: Part 4
51: Hollow fiber spinning nozzle
511: First nozzle
512: second nozzle
513: Support passage
514:
515:
516:
517:
518:
61, 62: hollow fiber spinning nozzle
611, 621: first nozzle
612, 622: second nozzle
613, 623: support passage
614, 624:
615, 625:
616, 626:
617, 627:
618, 618A, 619, 628:
71: Hollow fiber spinning nozzle
711: First nozzle
712: Second nozzle
713: third nozzle
714: Support passage
715, 722:
716, 723, 729:
717, 724:
718, 728:
719, 726:
730:

Claims (25)

A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer and a support,
Wherein the nozzle has a resin flow path for flowing a film-forming resin solution forming the porous film layer,
Wherein the resin flow path has a liquid storage portion for storing the film-forming resin solution and a shaping portion for shaping the film-forming resin solution into a cylindrical shape,
Wherein the liquid storage portion or the negative portion includes branching and merging means of the film-forming resin solution,
Wherein the branching and merging means is a porous element through which the film-forming resin solution, which is provided inside the liquid storage portion, passes through. The hollow fiber spinning nozzle according to claim 1, wherein the liquid storage portion is an annular circular ring. The hollow fiber spinning nozzle according to claim 1 or 2, wherein the resin flow channel has two or more joining portions joining the film-forming resin solution. delete The hollow fiber spinning nozzle according to claim 1, wherein the porous element has a three-dimensional mesh structure. The hollow fiber spinning nozzle according to claim 1, wherein the porous element is cylindrical. The hollow fiber spinning nozzle according to claim 1, wherein the cylindrical porous element is disposed so that the film-forming resin solution passes from the outer circumferential surface to the inner circumferential surface. The hollow fiber spinning nozzle of claim 1, wherein the porous element is in the shape of a disk. The hollow fiber spinning nozzle according to claim 1, wherein the porous element is made of a sintered metal. The hollow fiber spinning nozzle according to claim 9, wherein the porous element comprises a sintered body of metal fine particles or a sintered body of a wire mesh laminate. The hollow fiber spinning nozzle according to claim 1 or 2, wherein the hollow fiber spinning nozzle further has a circular support passage through which the support passes,
Wherein the diameter of the support passage is 95% to 200% of the outer diameter of the support. The hollow fiber spinning nozzle as claimed in claim 1 or 2, wherein the support comprises a braid or knit braid. The hollow fiber spinning nozzle according to claim 1 or 2, wherein the hollow fiber spinning nozzle comprises at least two liquid storage portions for storing a film-forming resin solution, and at least two resin liquid storage portions each having two or more resin portions having a cylindrical portion- Lt; / RTI &
Wherein the branching and joining means is the porous element provided in each of the liquid storage portions. The hollow fiber spinning nozzle according to claim 1 or 2, wherein the number of the calculated joins in the annular section of the hollow fiber membrane is 50 or more. The film forming apparatus according to claim 1, further comprising a discharge port through which the film-forming resin solution is discharged,
The pressure loss when the film-forming resin solution passes through the porous element is lower than the pressure loss until the film-forming resin solution reaches the porous element and the pressure loss until the film-forming resin solution passes through the porous element Is larger than the pressure loss from the nozzle to the outlet until reaching the discharge port. delete delete A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer and a support,
Wherein the nozzle has a resin flow path for flowing a film-forming resin solution forming the porous film layer,
Wherein the resin flow path has a liquid storage portion for storing the film-forming resin solution and a shaping portion for shaping the film-forming resin solution into a cylindrical shape,
Wherein the resin flow path is disposed so that the film-forming resin solution branches and merges,
Wherein the resin flow path has a liquid reservoir portion divided into two or more stages in the upper and lower portions,
Wherein the upper liquid storage portion and the liquid storage portion immediately below the liquid storage portion are communicated by the resin supply portion. The liquid storage apparatus according to claim 18, wherein the liquid storage section is divided into three or more stages, a resin supply section for connecting the n-th stage (n is a natural number) liquid storage section and the (n + 1) th stage liquid storage section, And the n + 2-th stage liquid storage portion is disposed at a position shifted in the circumferential direction of the liquid storage portion. 19. The hollow fiber spinning nozzle according to claim 18, wherein each of the resin supply portions is disposed at a predetermined angular interval in the circumferential direction of the liquid storage portion with respect to the central axis of the tubular portion in order from the top side. A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer and a support,
Wherein the nozzle has a resin flow path for flowing a film-forming resin solution forming the porous film layer,
Wherein the resin flow path has a liquid storage portion for storing the film-forming resin solution and a shaping portion for shaping the film-forming resin solution into a cylindrical shape,
The resin flow path is provided with a delay means for delaying the flow of the film-forming resin solution,
Wherein said retarding means is a skew portion between said liquid storage portion and said negative portion for causing said film-forming resin solution to skew upward and downward. A hollow fiber spinning nozzle for spinning a hollow fiber membrane having a porous membrane layer and a support,
Wherein the nozzle has a resin flow path for flowing a film-forming resin solution forming the porous film layer,
Wherein the resin flow path has a liquid storage portion for storing the film-forming resin solution and a shaping portion for shaping the film-forming resin solution into a cylindrical shape,
Wherein the resin flow path is disposed so that the film-forming resin solution branches and merges,
Wherein the resin flow path is provided so as to extend from one wall surface in the liquid storage portion toward the other wall surface, and wherein the resin flow path is provided in the liquid storage portion so that circulation of the film- Desert Spray Nozzle. A method for producing a hollow fiber membrane having a hollow porous membrane layer and a support,
Spinning a hollow hollow fiber membrane from the film-forming resin solution,
Coagulating the spun hollow fiber membrane by coagulating liquid,
Removing the solvent from the coagulated hollow fiber membrane,
Decomposing the additive in the hollow fiber membrane from which the solvent has been removed to clean the hollow fiber membrane,
Drying the hollow fiber membrane after cleaning, and
The hollow fiber membrane spinning nozzle according to any one of claims 1, 18, 21, and 22 is used for spinning the hollow fiber membrane from the film- And the hollow fiber membrane is radiated. The hollow fiber membrane according to claim 23, wherein an outer diameter d of the hollow fiber membrane emitted in the spinning of the hollow fiber membrane is 0.5 mm or more and 5.0 mm or less,
Wherein the value d / dh obtained by dividing the outer diameter d of the hollow fiber membrane by the inner diameter dh is not less than 1.3 and not more than 5.0. 24. The method of producing a hollow fiber membrane according to claim 23, wherein the calculated number of confluent filaments in the annular cross section of the hollow fiber membrane spun in the spinning of the hollow fiber membrane is 50 or more.

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